DE112019000516B4 - Sole structure for an article of footwear and article of footwear - Google Patents

Abstract

Sole structure with a sheet containing a polyolefin resin, in which the polyolefin resin composition comprises a polyolefin copolymer and an effective amount of a polymer resin modifier, in which the effective amount of the polymer resin modifier, based on a total weight of the resin composition, is about 5% to about 30%, in which the polymer resin modifier is a copolymer comprising isotactic propylene repeat units and ethylene repeat units, and wherein the polymer resin modifier comprises from about 10% to about 15% ethylene repeat units based on the total weight of the polymer resin modifier.

Description

The present disclosure relates to a sole structure for an article of footwear such as footwear and an article of footwear.

The EP 1 820 821 A1 discloses materials for footwear. The U.S. 3,851,411A discloses a shoe having a counter or heel counter formed from a blend of a monoolefin copolymer rubber and a polyolefin plastic.

The design and manufacture of footwear and sports equipment involves a number of factors such as aesthetics, comfort and feel, as well as function and durability. While style and fashion may change rapidly, the need for improved functionality remains in the footwear and sporting goods market. In addition, the market has shifted towards demands for low cost and recyclable materials, while at the same time increasing demands for functionality.

The sole structure of claim 1 and the article of footwear of claim 13 help meet these needs.

Further developments are specified in the dependent claims.

• 1A-1H zeigen einen beispielhaften Sportschuh. 1A ist eine perspektivische Seitenansicht des beispielhaften Sportschuhs. 1B ist eine Seitenansicht des beispielhaften Sportschuhs von außen. 1C ist eine Seitenansicht des beispielhaften Sportschuhs von innen.
• 1D ist eine Draufsicht des beispielhaften Sportschuhs von oben. 1E ist eine Vorderansicht des beispielhaften Sportschuhs. 1F ist eine Rückansicht des beispielhaften Sportschuhs. 1G ist eine perspektivische Explosionsansicht des beispielhaften Sportschuhs. 1H ist eine Schnittansicht des beispielhaften Sportschuhs entlang Linie 1-1.
• 2A-2C zeigen einen zweiten beispielhaften Sportschuh. 2A ist eine Seitenansicht des beispielhaften Sportschuhs. 2B ist eine perspektivische Explosionsansicht des zweiten beispielhaften Sportschuhs. 2C ist eine Schnittansicht des zweiten beispielhaften Sportschuhs entlang Linie 2-2.
• 3 zeigt eine Explosionsansicht einer dritten beispielhaften Sohlenkonstruktion mit einem Rahmen und einer starren Platte, wodurch Stabilität bereitgestellt wird, ohne wesentliche Mengen von zusätzlichem Material zu benötigen, wodurch daher ein niedriges Gewicht beibehalten wird.
• 4A-4C zeigen einen vierten beispielhaften Sportschuh. 4A ist eine Seitenansicht des beispielhaften Sportschuhs. 4B ist eine perspektivische Explosionsansicht des zweiten beispielhaften Sportschuhs. 4C ist eine Schnittansicht des zweiten beispielhaften Sportschuhs entlang Linie 4-4.
• 5A-5B zeigen einen fünften beispielhaften Sportschuh. 5A ist eine Seitenansicht des fünften beispielhaften Sportschuhs. 5B ist eine perspektivische Explosionsansicht des fünften beispielhaften Sportschuhs.

Other aspects of the present disclosure are apparent from the detailed description given below in connection with the accompanying drawings.

• 1A-1H show an exemplary sports shoe. 1A Figure 12 is a side perspective view of the exemplary athletic shoe. 1B Figure 12 is an external side view of the example athletic shoe. 1C 12 is an inside side view of the exemplary athletic shoe.
• 1D 12 is a top plan view of the exemplary athletic shoe. 1E 12 is a front view of the exemplary athletic shoe. 1F Figure 12 is a rear view of the exemplary athletic shoe. 1G 12 is an exploded perspective view of the exemplary athletic shoe. 1H 12 is a sectional view of the exemplary athletic shoe taken along line 1-1.
• 2A-2C show a second exemplary sports shoe. 2A Figure 12 is a side view of the exemplary athletic shoe. 2 B 12 is an exploded perspective view of the second exemplary athletic shoe. 2C 12 is a sectional view of the second exemplary athletic shoe taken along line 2-2.
• 3 Figure 12 shows an exploded view of a third exemplary sole construction having a frame and rigid plate that provides stability without requiring significant amounts of additional material, thus maintaining low weight.
• 4A-4C show a fourth exemplary athletic shoe. 4A Figure 12 is a side view of the exemplary athletic shoe. 4B 12 is an exploded perspective view of the second exemplary athletic shoe. 4C Figure 4 is a sectional view of the second example athletic shoe taken along line 4-4.
• 5A-5B show a fifth exemplary athletic shoe. 5A 12 is a side view of the fifth exemplary athletic shoe. 5B 12 is an exploded perspective view of the fifth exemplary athletic shoe.

DETAILED DESCRIPTION

Known special polymers for footwear and sporting goods are polymers such. B. polyurethane and polyamide polymers, but there remains a need for lower cost alternatives to these performance polymers, particularly lower cost alternatives that are recyclable and have good processability. alternatives such as B. Polyolefins, while inexpensive, have traditionally had poor mechanical properties and unsuitable surface energies for assembly. New constructions and materials are needed. In particular, there is a need for improved polymeric resins for making footwear and sporting goods components that are resistant to stress whitening or cracking when flexed under cold conditions, that are resistant to wear, and that allow adequate assembly for footwear and other sporting goods applications.

In various aspects, this disclosure provides sole constructions with a sheet containing a polyolefin resin. In some aspects, the sole constructions include the plate and a textile material on one or more surfaces of the disk. The textile material can improve the attachment of other components (e.g. a top or a frame) to the panel. The textile material can also be used for decorative purposes. Sheets containing the polyolefin resin compositions can exhibit improved mechanical properties, making them particularly suitable for use in footwear and sporting goods components. In particular, these resin compositions are resistant to both stress whitening and cracking when flexed under cold conditions and are resistant to wear to the degree required for use in footwear and sporting goods. The present disclosure provides a variety of footwear sheets containing these polyolefin resin compositions.

In some aspects, this disclosure provides a sole construction for an article of footwear, the sole construction comprising a sheet containing a polyolefin resin, the sheet having a first side and a second side, the first side being configured to contact the ground when the sheet is a is a component of an article of footwear and wherein a textile material is disposed on one or both of the first side and the second side. In some aspects, the sole construction further includes a framework configured to be on the first side of the plate. The welt may be wrapped around the plate and engaged or attached to an upper where the sole construction is a component of an article of footwear, for example the welt may be attached to the upper at the welt seam. In some aspects, the sole constructions do not contain textile material, e.g. eg, the sole construction may comprise the plate and a frame as described in more detail above and below.

In various aspects, this disclosure also provides footwear having a sole construction as described herein.

Before the present disclosure is described in more detail, it should be understood that this disclosure is not limited to the particular aspects described and as such may, of course, vary. Other systems, methods, features and advantages of resin compositions and articles and components thereof will become apparent to those skilled in the art upon review of the following drawings and detailed description. All such other systems, methods, features, and advantages described in this specification are intended to be within the scope of the present disclosure and protected by the appended claims. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. Those skilled in the art will recognize numerous variations and adaptations of the aspects described herein. These variations and adaptations are intended to be included within the teachings of this disclosure and covered by the claims herein.

Sole structures and articles of footwear made therefrom

In some aspects, the present disclosure is directed to sole constructions having a sheet containing a polyolefin resin. The present disclosure also contemplates footwear incorporating the sole constructions. As discussed below, the sheets containing the polyolefin resin compositions desirably exhibit high levels of mechanical strength and yet flex toughness. However, applicants have found that in some aspects when polyolefin resin compositions are used in the panels, bonding to a surface of the panel (e.g., bonding the panel to the top) may not be satisfactory. Thus, in some aspects, the sole constructions include the plate and a textile material disposed on one or more surfaces of the plate. Without being bound by any particular theory, it is believed that providing the textile material on one or more surfaces of the panel can result in an improved bond between the panel and the top, particularly when the top is formed from a different polymeric resin than the panel . In one example, using a textile material comprising fibers or yarns of a polymeric material having a different surface energy than the surface energy of the polyolefin resin of the panel may facilitate attachment to an upper comprising a polymeric material having a surface energy closer to the surface energy of the textile material than that surface energy of the polyolefin resin of the panel, thereby increasing the strength of a bond between the panel and the top compared to a panel without the fabric. Using a textile material can result in a textured surface with a larger surface area, which provides a greater chance for mechanical connections to form between the top and the panel, thereby increasing the strength of a connection between the top and the top compared to a panel without the Textile material is increased. This can be another benefit Textile material can be used to provide a decorative or stylish finish in some aspects.

1A 12 is a side perspective view of an exemplary cleated athletic shoe 110, such as a soccer shoe. how to get in 1A 1, the article of footwear 110 includes an upper 112 and a sole construction 113 comprising a plate 116 and a textile material 114 disposed on the upper side 152 of the plate of the article of footwear. The textile material 114 is located between the plate 116 and the upper 112. The plate 116 has a plurality of traction elements (lugs) 118 thereon. In use, the traction elements 118 provide traction for a user, which improves stability. One or more of the traction elements 118 can be formed integrally with the plate, as in FIG 1A shown, or they may be removable. Optionally, one or more of the traction elements 118 may include a tip on the traction element (not shown) that is configured to contact the ground. The tip of the traction element may be formed integrally with the traction element 118 . Optionally, the tip of the traction element may be formed from a different material (e.g., a metal or a polymeric material containing other polymers) than the remainder of the traction element 118 . 1B 12 is an external side view of the article of footwear 110. FIG. When the article of footwear 110 is worn, the outer side of the article 110 is generally oriented on the side away from the midline of the user's body. 1C 12 is an inside side view of the article of footwear 110. FIG. When the article of footwear 110 is worn, the inner side generally faces the midline of the user's body. 1D 12 is a plan view of the article of footwear 110 (without the insole) and without an insole or other sole-like element 115 and further including the upper 112. FIG. The upper part 112 has a padded collar 120 . Alternatively or additionally, the upper may include a portion configured to extend to or beyond the user's ankle (not shown). In at least one aspect, the upper 112 does not have a tab, wherein the upper wraps over the upper of the foot and under the lateral side portion of the upper from the inner side of the user's foot, as shown in FIG 1D shown. Alternatively, the article of footwear may include a tongue (not shown). As in 1A-1G As shown, the laces of the article of footwear 110 can optionally be on the outer side of the article. In other examples, the article of footwear may have a slip-on design or a closure system other than laces (not shown). 1E and 1F are front and back views, respectively, of article 110 of footwear.

1G Figure 12 is an exploded perspective view of the article of footwear 110 showing the upper 112, the plate 116 and the textile material 114. FIG. how to get in 1D sees, the upper part 112 has a strobel element 138 . As in 1D As shown, the strobel 138 is generally in the shape of the user's foot and completes the bottom of the upper 112 and is sewn to other components to form the upper 112 along the perimeter of the strobel 138 at seam 185 . An insole or other sole-like element 115 may be located over or under the strobel element 138 . In some aspects, an insole or other sole-like element can replace the strobel element. The insole or other sole-like element 115 may extend substantially the entire length of the plate, or may be present in a portion of the length of the plate, such as in the toe region 130 or in the midfoot region or in the heel region. The top 112 having the strobel element 138 is bonded to the top surface 140 of the fabric 114 ( 1G-1H) . The lower surface 142 of the fabric 114 may be bonded or fused to the surface 152 of the top of the panel 116 . In some aspects, the lower surface 142 of the fabric 114 may be mechanically bonded to the upper surface 152 of the panel 116 by fusing polymers in the fabric 114 and the polymeric resin of the panel 116 . Alternatively or additionally, the top 112 having the strobel 138 is mechanically bonded to the top surface 140 of the fabric 114 by fusing the polymeric resin of the top 112 or the strobeled element 138 with the polymeric resin of the plate 116 . In some aspects, the bonding may include both adhesive bonding and mechanical bonding.

In at least one aspect, the plate 116 and the fabric 114 are first bonded before the upper 112 and/or the strobel 138 is/are bonded to the fabric 114 . In some aspects, the article of footwear 110 may include a removable insole (not shown). As is well known in the art, an insole conforms to and lines the inner subsurface of a shoe and is the component that is contacted by the sole (or sole with sock) of the user.

2A-2C show a second exemplary sports shoe. 2A Figure 12 is an external side view of the example athletic shoe. 2 B Fig. 14 is an exploded perspective view of the second example adhere to sports shoes. 2C 12 is a sectional view of the second exemplary athletic shoe taken along line 2-2. 2A Figure 2 is a side view of an exemplary article of footwear 210 that does not include textile material. Article of footwear 210 includes an upper 212 and sole construction 213 having a plate 216 and chassis 217 . The frame 217 has multiple traction elements 218 . The traction elements 218 can be formed entirely from the material of the frame 217 or, as in 2 B As illustrated, traction members 118 may include a corresponding inner traction member 219 formed in plate 216 and surrounded by frame 217 . Optionally, one or more of the traction elements 218 may include a tip on the traction element (not shown) configured to contact the ground. The article of footwear 210 may include an insole member 215 that may extend substantially the entire length of the panel 216 .

In some aspects, the sole construction can include a plate to provide rigidity, strength, and/or support without adding substantial weight. For example, some example aspects of the sole construction may include a plate with certain features that provide resistance to vertical flexing, lateral flexing, and/or torsion. As in 3 As shown, the panel 300 may include a reinforcing rib 310 longitudinally along the panel. The reinforcing rib can have a hollow structure and thus provide strength without adding significant amounts of additional material, thereby maintaining a low weight. The plate 300 can be accommodated in a frame 330, for example with a recess 320 in the frame 330.

In some aspects, when the sole construction comprises a plate and a frame configured to be wrapped around the plate and engage or be attached to an upper when the sole construction is a component of an article of footwear, the Sole construction also one or more textile materials. For example, a fabric may be provided between the panel and the top and may provide an improved bond between the panel and the top. A textile material can also be arranged between the plate and the frame. In aspects where the fabric is between the panel and the frame, the fabric may provide improved adhesion between the panel and the frame, and/or the fabric may be a decorative or fancy fabric. In some aspects, the sole construction may include a decorative textile material on the outer or ground-facing surface of the welt. For example, as in 4A-4C As shown, the article of footwear 410 includes an upper 412 and sole construction 413 having a plate 416 and chassis 417 . The frame 417 has multiple traction elements 418 . Traction members 418 may be formed entirely from the material of frame 417, as shown. Optionally, one or more of the traction elements 418 may include a tip on the traction element (not shown) configured to contact the ground. A textile material 414 is located between the plate 416 and the frame 417. The article of footwear 410 may include an insole element 415 which may extend the plate 416 substantially the entire length.

5A 12 is a side view of an exemplary article of footwear 510 having a separate heel plate 515, metatarsal plate 516, and toe plate 517. Article of footwear 510 includes an upper 512 and heel plate 515, metatarsal plate 516, and toe plate 517. FIG. Each of the heel plate 515 , metatarsal plate 516 and toe plate 517 has multiple traction elements 518 . In use, the traction elements 518 provide traction for a user so as to increase stability. One or more of the traction elements 518 may be integrally formed with the heel plate 515, midfoot plate 516 and/or toe plate 517, as shown in FIG 5A shown, or they may be removable. 5B Figure 5 is an exploded perspective view of article of footwear 510 showing upper 512, heel plate 515, metatarsal plate 516, and toe plate 517. FIG. In this aspect, the upper surface 525 of the heel plate 515 may include a heel textile 535 . The top surface 527 of the toe plate 517 may include a toe textile 537 . Likewise, the upper surface 526 of the midfoot plate 516 includes a midfoot fabric 536 . The textile materials can provide an improved connection between upper 512, heel plate 515, metatarsal plate 516 and toe plate 517.

This disclosure contemplates a variety of sole constructions including a polyolefin sheet, ie, including a sheet composition containing a polyolefin resin. The panel comprises a polyolefin resin composition, for example any of the polyolefin resin compositions described herein. The sole constructions may also comprise an elastomeric material containing a cured rubber and a hydrogel material, in the elastomeric material the hydrogel material is dispersed in the cured rubber, and at least a portion of the hydrogel material in the elasto material is physically encapsulated within the cured rubber. Such systems are disclosed in US Provisional Patent Application 62/574,262 entitled "RUBBER COMPOSITIONS AND USES THEREOF" filed on 10/19/2017, the contents of which are incorporated herein by reference in their entirety as if fully disclosed herein, their priority in the WO 2019/ 079 715 A1 is claimed. The elastomeric materials can provide anti-clog properties.

The sole constructions may include a textile material on one or more surfaces of the plate. For example, when the panel has a first side and a second side, the first side can be configured to face the ground when the panel is a component of an article of footwear, and the second side can be configured to face upward point. In some aspects, the fabric is on one or both of the first side and the second side. The textile material can provide an improved connection between the plate and other components of the sole construction, e.g. B. between the plate and a frame. The textile material can also provide an improved connection between the plate and the upper when the sole construction is a component of an article of footwear. In some aspects, the fabric is a textured or decorative fabric.

In some aspects, the sole constructions include a welt. In some aspects, the welt is combined with one or more textile materials in the sole construction, while in some aspects the sole construction includes a welt and no textile material. The frame can be configured to be on the first side or on the ground-facing side of the panel. In some aspects, the frame is configured to be wrapped around the plate and engaged or attached to an upper when the sole construction is a component of an article of footwear. The frame can be attached to the bodice at the frame seam.

In some aspects, the traction elements are made of the same or nearly the same polyolefin resin composition as the panel. In other aspects, the traction elements are made of a second resin that is different than the polyolefin resin. In some aspects, the sole construction includes a frame, and the frame is made of the second resin. The second resin may be a polystyrene, a polyethylene, an ethylene-α-olefin copolymer, an ethylene-propylene rubber (EPDM), a polybutene, a polyisobutylene, a poly-4-methylpent-1-ene, a polyisoprene polybutadiene, an ethylene-methacrylic acid copolymer, an olefin elastomer, a copolymer thereof, or a blend or blend thereof. In some aspects, the second resin comprises about 20%, about 10%, or less of a polyolefin. The second resin can comprise about 20%, about 10% or less of polypropylene. The second resin may comprise an ethylene propylene rubber (EPDM) dispersed in a polypropylene. The second resin may comprise a block copolymer comprising a polystyrene block. The included block copolymer can be, for example, a copolymer of styrene and one or both of ethylene and butylene. In general, the second resin can be any resin that is compatible with the polyolefin resin and that has the appropriate durability and mechanical properties.

In particular, it has been found that the second resin (e.g., a polystyrene, a polyethylene, an ethylene-α-olefin copolymer, an ethylene-propylene rubber (EPDM), a polybutene, a polyisobutylene, a poly-4 -methylpent-1-ene, a polyisoprene, a polybutadiene, an ethylene-methacrylic acid copolymer, an olefin elastomer, a copolymer thereof, or a blend or mixture thereof) combines well with the resin compositions of the present disclosure.

Furthermore, it has been found that second resins containing an ethylene-propylene rubber (EPDM) dispersed in a polypropylene or a block copolymer with a polystyrene block, the block copolymer having a copolymer of styrene and one or both of ethylene and butylene, in particular in the ground-contacting areas of the traction members, since these compositions bond well with the resin compositions of the present disclosure and can provide an even higher level of wear resistance than the resin compositions of the present disclosure, which is desirable for the ground-contacting areas of the traction members can be.

In some aspects, it may be advantageous to include a clarifying agent in the panel (in the polyolefin resin) and/or, if a frame is present, in the frame. The clearing agent can provide clear visibility of a fabric through the panel. The clarifying agent can be present in any suitable amount to provide sufficient optical clarity of the final plate or sole construction. In some aspects, the clarifier is present in an amount from about 0.5% to about 5%, or from about 1.5% to about 2.5% by weight based on a total weight of the polyolefin resin. The clarifier can be selected from the group consisting of substituted or unsubstituted dibenzylidene sorbitol, 1,3-O-2,4-bis(3,4-dimethylbenzylidene) sorbitol, 1,2,3-trideoxy-4,6:5,7 -bis-O-[(4-propylphenyl)methylene] and a derivative thereof. The clarifying agent may comprise an acetal compound which is the condensation product of a polyhydric alcohol and an aromatic aldehyde. The polyhydric alcohol can be selected from the group consisting of acyclic polyols such as e.g. B. xylitol and sorbitol and acyclic deoxypolyols such as. 1,2,3-trideoxynonitol or 1,2,3-trideoxynon-1-enitol. The aromatic aldehyde can be selected from the group consisting of benzaldehyde and substituted benzaldehydes.

resin compositions

A variety of resin compositions provide the wear resistance and flex life suitable for use in the articles and components described above. In some aspects, a resin composition including a polyolefin copolymer and an effective amount of a polymer resin modifier is provided. The effective amount of resin modifier provides improved flex durability while maintaining adequate wear resistance. For example, in some aspects, the effective amount of the polymeric resin modifier is an amount effective for the resin composition to pass a flex test according to the Ross cold flex test using the plaque sampling method. At the same time, the resin composition can still exhibit a suitable wear loss when measured according to ASTM D 5963-97a using the material sampling method. In some aspects, the resin composition, which is otherwise the same except for the lack of polymer resin modifier, fails the Ross cold flex test using the material sampling method.

The polymer resin modifier can provide improved flexural strength, toughness, creep resistance, or durability in flexing without a significant loss in wear resistance. In some aspects, a resin composition is provided with a polyolefin copolymer and an effective amount of a polymer resin modifier, wherein the effective amount of the polymer resin modifier is an amount effective for the resin composition to pass a flex test according to the Ross cold flex test using the plaque sampling method without a significant change a wear loss compared to a wear loss of a second resin composition identical to the resin composition except for the absence of the polymeric resin modifier when measured according to ASTM D 5963-97a using the material sampling method. In other words, in some aspects, the effective amount of the polymeric resin modifier is an amount that is sufficient to produce a resin composition that is not subject to stress whitening or cracking during 150,000 flex cycles of the Ross Cold Bend Test while not significantly degrading the wear resistance of the resin composition and thus is not significantly different from the wear resistance of a comparative resin composition which is otherwise identical to the resin composition except that it does not contain the polymeric resin modifier.

In some aspects, the resin composition has an attrition loss of from about 0.05 cubic centimeters (cm ³ ) to about 0.1 cubic centimeters (cm ³ ), about 0.07 cubic centimeters (cm ³ ) to about 0.1 cubic centimeters (cm ³ ), about 0.08 cubic centimeters (cm ³ ) to about 0.1 cubic centimeters (cm ³ ) or about 0.08 cubic centimeters (cm ³ ) to about 0.11 cubic centimeters (cm ³ ) according to ASTM D 5963-97a using the material sampling method. In some aspects, the resin composition exhibits no significant change in wear loss compared to a wear loss of a second resin composition identical to the resin composition except for the lack of polymer resin modifier when measured according to ASTM D 5963-97a using the material sampling method. A change in wear loss, as used herein, is not significant if the change when measured according to ASTM D 5963-97a using the material sampling method is about 30%, about 25%, about 20%, about 15%, about 10% or less .

The resin compositions may contain a plurality of polyolefin copolymers. The copolymers can be alternating copolymers, or random copolymers, or block copolymers, or graft copolymers. In some aspects, the copolymers are random copolymers. In some aspects, the copolymer has a plurality of repeat units, each of the plurality of repeat units being individually derived from an alkene monomer having from about 1 to about 6 carbon atoms. In In other aspects, the copolymer has a plurality of repeating units, each of the plurality of repeating units being individually selected from a monomer from the group consisting of ethylene, propylene, 4-methyl-1-pentene, 1-butene, 1-octene and a Combination thereof is derived. In some aspects, the polyolefin copolymer has a plurality of repeating units each individually selected from Formulas 1A-1D. In some aspects, the polyolefin copolymer has a first plurality of repeating units having a structure according to Formula 1A and a second plurality of repeating units having a structure selected from Formula 1B-1D.

wobei R¹ Wasserstoff oder ein substituiertes oder unsubstituiertes, lineares oder verzweigtes C₁-C₁₂-Alkyl, C₁-C₆-Alkyl, C₁-C₃-Alkyl, C₁-C₁₂-Heteroalkyl, C₁-C₆-Heteroalkyl oder C₁-C₃-Heteroalkyl ist. In einigen Aspekten hat jede der Wiederholungseinheiten in der ersten Mehrzahl von Wiederholungseinheiten eine Struktur gemäß Formel 1A weiter oben, und jede der Wiederholungseinheiten in der zweiten Mehrzahl von Wiederholungseinheiten hat eine Struktur gemäß Formel 2 weiter oben.In some aspects, the polyolefin copolymer has a plurality of repeating units each having a structure according to Formula 2, individually

where R ¹ is hydrogen or a substituted or unsubstituted, linear or branched C ₁ -C ₁₂ alkyl, C ₁ -C ₆ alkyl, C ₁ -C ₃ alkyl, C ₁ -C ₁₂ heteroalkyl, C ₁ -C ₆ -heteroalkyl or C ₁ -C ₃ -heteroalkyl. In some aspects, each of the repeat units in the first plurality of repeat units has a structure according to Formula 1A above, and each of the repeat units in the second plurality of repeat units has a structure according to Formula 2 above.

In some aspects, the polyolefin copolymer is a random copolymer of a first plurality of repeating units and a second plurality of repeating units, and each repeating unit in the first plurality of repeating units is derived from ethylene and each repeating unit in the second plurality of repeating units is derived from one second olefin derived. In some aspects, the second olefin is an alkene monomer having from about 1 to about 6 carbon atoms. In other aspects, the second olefin includes propylene, 4-methyl-1-pentene, 1-butene, or other linear or branched terminal alkenes having from about 3 to 12 carbon atoms. In some aspects, the polyolefin copolymer contains from about 80% to about 99%, from about 85% to about 99%, from about 90% to about 99%, or from about 95% to about 99% polyolefin repeat units by weight based on a total weight of the polyolefin -copolymers. In some aspects, the polyolefin copolymer consists essentially of polyolefin repeating units. In some aspects, the polymers in the resin composition consist essentially of polyolefin copolymers.

The polyolefin copolymer may contain ethylene, i. H. may have repeating units derived from ethylene, such as e.g. B. those in Formula 1A. In some aspects, the polyolefin copolymer has from about 1% to about 5%, from about 1% to about 3%, from about 2% to about 3%, or from about 2% to about 5% ethylene by weight based on a total weight of the polyolefin copolymer on.

The resin compositions can be made without the need for polyurethanes and/or polyamides. For example, in some aspects the polyolefin copolymer is essentially free of polyurethanes. In some aspects, the polymer chains of the polyolefin copolymer are essentially free of urethane repeat units. In some aspects, the resin composition is essentially free of polymer chains having urethane repeat units. In some aspects, the polyolefin copolymer is essentially free of polyamide. In some aspects, the polymer chains of the polyolefin copolymer are essentially free of amide repeat units. In some aspects, the resin composition is essentially free of polymer chains having amide repeat units.

In some aspects, the polyolefin copolymer comprises or is a polypropylene copolymer. In some aspects, the polymer component of the resin composition (i.e., that portion of the resin composition formed by all of the polymers in the composition) consists essentially of polypropylene copolymers. In some aspects, the resin composition is provided with a polypropylene copolymer and an effective amount of a polymer resin modifier, wherein the resin composition has a wear loss as described above, and wherein the effective amount of the polymer resin modifier is an amount effective for the resin composition to have a Passes the Ross cold flex test using the plaque sampling method. In some aspects, the effective amount of the polymer resin modifier is an amount effective for the resin composition to pass a Ross cold flex flex test using the plaque sampling method without a significant change in wear loss compared to a wear loss of a second resin composition that is compatible with the resin composition is identical except for the lack of polymer resin modifier when measured according to ASTM D 5963-97a using the material sampling method.

The polypropylene copolymer may include a random copolymer, e.g. B. a random copolymer of ethylene and propylene. The polypropylene copolymer can have about 80% to about 99%, about 85% to about 99%, about 90% to about 99%, or about 95% to about 99% propylene repeat units by weight based on a total weight of the polypropylene copolymer . In some aspects, the polypropylene copolymer has about 1% to about 5%, about 1% to about 3%, about 2% to about 3%, or about 2% to about 5% ethylene by weight based on a total weight of the polypropylene copolymer on. In some aspects, the polypropylene copolymer is a random copolymer having from about 2% to about 3% of a first plurality of repeat units by weight and from about 80% to about 99% of a second plurality of repeat units by weight based on a total weight of the polypropylene copolymer; wherein each of the repeating units in the first plurality of repeating units has a structure according to Formula 1A above and each of the repeating units in the second plurality of repeating units has a structure according to Formula 1B above.

The combination of wear resistance and flexing toughness can be related to the overall crystallinity of the resin composition. In some aspects, the resin composition has a percent crystallization (% crystallization) of about 45%, about 40%, about 35%, about 30%, about 25% or less when measured according to the differential scanning calorimetry (DSC) test using the material sampling procedure. It has been found that adding the polymeric resin modifier to the resin composition in an amount that only slightly decreases the % crystallinity of the resin composition compared to a resin composition otherwise identical except for the absence of the polymeric resin modifier can result in resin compositions capable of to pass the Ross cold bend test while maintaining a relatively low wear loss. In some aspects, the polymeric resin modifier results in a decrease in the percent crystallinity (% crystallinity) of the resin composition. In some aspects, the resin composition has a percent crystallinity (% crystallization) that is at least 6, at least 5, at least 4, at least 3, or at least 2 percentage points less than a percent crystallinity (% crystallization) of the resin composition that is otherwise the same except for the missing polymer resin modifier when measured according to the differential scanning calorimetry (DSC) test using the material sampling method.

In some aspects, the effective amount of the polymer resin modifier is about 5% to about 30%, about 5% to about 25%, about 5% to about 20%, about 5% to about 15%, about 5% to about 10%, about 10% to about 15%, about 10% to about 20%, about 10% to about 25%, or about 10% to about 30% by weight based on a total weight of the resin composition. In some aspects, the effective amount of the polymeric resin modifier is about 20%, about 15%, about 10%, about 5% or less by weight based on a total weight of the resin composition.

The polymer resin modifier may include a variety of exemplary resin modifiers as described herein. In some aspects, the polymer resin modifier is a metallocene-catalyzed copolymer consisting primarily of isotactic propylene repeat units with about 11% to 15% by weight of ethylene repeat units based on a total weight of the metallocene-catalyzed copolymer randomly distributed along the copolymer is. In some aspects, the polymeric resin modifier has from about 10% to about 15% ethylene repeat units by weight based on a total weight of the polymeric resin modifier. In some aspects, the polymeric resin modifier has from about 10% to about 15% repeating units according to Formula 1A above by weight based on a total weight of the polymeric resin modifier. In some aspects, the polymeric resin modifier is a copolymer of repeating units according to Formula 1B above, and the repeating units according to Formula 1B are arranged in an isotactic stereochemical configuration.

In some aspects, the polymeric resin modifier is a copolymer containing isotactic propylene repeating units and ethylene repeating units. In some aspects, the polymer resin modifier is a copolymer having a first plurality of repeating units and a second plurality of repeating units, wherein each of the repeating units in the first plurality of repeating units has a structure according to Formula 1A above and each of the repeating units in the second plurality of repeating units has a Having a structure according to Formula 1B above and wherein the repeating units in the second plurality of repeating units are arranged in an isotactic stereochemical configuration.

hydrogel materials

In one aspect, the hydrogel material is a polyurethane hydrogel. The hydrogel material can be a polyamide hydrogel, a polyurea hydrogel, a polyester hydrogel, a polycarbonate hydrogel, a polyetheramide hydrogel, a hydrogel formed from addition polymers of ethylenically unsaturated monomers, copolymers thereof (e.g. co- polyesters, co-polyethers, co-polyamides, co-polyurethanes, co-polyolefins) and combinations thereof. More details are listed here.

The term "outward facing" as used in the phrase "outward facing layer" refers to the position that the element is intended to occupy when the element is present in an article in normal use. If the article is footwear, in normal use the element will be positioned by a wearer in a standing position towards the ground and may thus contact the ground, including unpaved surfaces, when the footwear is used in a conventional manner, e.g. B. Standing, walking or running on unpaved surfaces. In other words, even though the element need not necessarily face the ground during the various manufacturing or shipping steps, if the element is intended to face the ground during normal use by a wearer, the element is considered to be outward-facing or, more specifically for an article of footwear, understood as facing the ground. Under certain circumstances, the outward-facing (e.g. ground-facing) surface may be discolored due to the presence of elements such as e.g. B. tension elements are positioned towards the ground in conventional use, but does not necessarily have to come into contact with the ground. For example, on hard ground or paved surfaces, the ends of the traction elements on the outsole may directly touch the ground, while portions of the outsole that are between the traction elements do not. As described in this example, the portions of the outsole that are between the traction elements are considered outward-facing (e.g., facing the ground) even though they may not directly touch the ground under all circumstances.

It has been found that the sheet material and articles incorporating the sheet material (e.g., footwear) can prevent or reduce the build-up of dirt on the facing layer of the sheet material during wear on unpaved surfaces. As used herein, the term "ground" can include any of a variety of materials commonly present on a ground or playing surface that might otherwise adhere to an outsole or exposed midsole of an article of footwear. The subsoil can contain inorganic materials such as mud, sand, dirt and gravel, organic matter such as grass, turf, leaves, other vegetation and excrement, and combinations of inorganic and organic materials such as clay. In addition, the subsurface may contain other materials such as powdered rubber which may be present on or in an unpaved surface.

Without wishing to be bound by theory, it is believed that the layered material (e.g., the hydrogel material) in accordance with the present disclosure when sufficiently wetted with water (including water containing dissolved, dispersed, or otherwise suspended materials ), can cause compressive compliance and/or expulsion of the absorbed water. In particular, it is suspected that the compressive compliance of the wet layer material, the expulsion of liquid from the wet layer material, or both in combination, can disrupt the adhesion of the subsurface on or to the outsole or the cohesion of the particles with one another or both adhesion and cohesion. It is believed that this disruption of the adhesion and/or cohesion of the ground is the reason that the ground (due to the presence of the wet material) does not accumulate (or otherwise reduce) on the outsole of the shoe.

It is believed that this disruption of the adhesion and/or cohesion of the ground causes the ground (due to the presence of the layered material) not to accumulate (or otherwise reduce) on the outsole of the shoe. As can be seen, preventing subsoil buildup on the bottom of shoes can improve the performance of the traction elements on the outsole during wear on unpaved surfaces, prevent weight gain of the shoes from subsoil buildup during wear, preserve the heel capacity of the shoes, and thus provide the wearer with significant Provide benefits compared to footwear without the material present on the outsole.

In aspects where the sheet material (e.g., hydrogel material) swells, the swelling of the sheet material may occur as an increase in material thickness from the thickness of the sheet material when dry, through a series of intermediate state thicknesses as additional water is absorbed, and eventually to a Saturated state bed material can be observed, which represents an average thickness of the bed material when fully saturated with water. For example, the saturated state thickness for the fully saturated layer material may be greater than 150%, greater than 200%, greater than 250%, greater than 300%, greater than 350%, greater than 400%, or greater than 500% of the thickness in dry state for the same sheet material (e.g. the hydrogel material) as characterized by the swellability test. In some aspects, the saturated state thickness for the fully saturated sheet material can be about 150% to 500%, about 150% to 400%, about 150% to 300%, or about 200% to 300% of the dry state thickness for the same sheet material be. Examples of suitable average thicknesses for the sheet material when wet (referred to as saturated thickness) may be about 0.2 millimeters to 10 millimeters, about 0.2 millimeters to 5 millimeters, about 0.2 millimeters to 2 millimeters, about 0. 25 millimeters to 2 millimeters or about 0.5 millimeters to 1 millimeter.

In certain aspects, the sheet material in neat form can exhibit a caliper increase after 1 hour of about 35% to 400%, about 50% to 300%, or about 100% to 200% as characterized by the swellability test. In some other embodiments, the sheet material in clean form can exhibit an increase in thickness of about 45% to 500%, about 100% to 400%, or about 150% to 300% after 24 hours. Accordingly, the outsole film in clean form may exhibit an increase in film volume at 1 hour of about 50% to 500%, about 75% to 400%, or about 100% to 300%.

In particular aspects, the sheet material can rapidly absorb water that is in contact with the sheet material. For example, the sheet material can absorb water from mud and wet grass, such as during warm-up before a competitive game. Alternatively (or in addition) the sheet material may be pre-treated with water so that the sheet material is partially or fully saturated, e.g. B. by spraying or soaking the sheet material with water before use.

In particular aspects, the sheet material can have an overall water absorption capacity of about 25% to 225% as measured in the water absorption capacity test over a 24 hour soak time using the component sampling method as defined below. Alternatively, the total water capacity of the sheet material ranges from about 30% to about 200%, alternatively about 50% to about 150%, alternatively about 75% to about 125%. For purposes of this disclosure, the term "total water holding capacity" is used to represent the amount of water held by the sheet material as a percentage by weight of the dry sheet material. The procedure for measuring the total water absorption capacity involves measuring the “dry” weight of the sheet material, immersing the sheet material in water at ambient temperature (~23°C) for a predetermined period of time, followed by re-measuring the weight of the sheet material in the "wet" state. The following describes the method of measuring the total weight holding capacity after the water holding capacity test using the component sampling method.

In one aspect, the sheet material can also be characterized by a water uptake rate of from 10 g/m ² /√min to 120 g/m ² /√min measured in the water uptake test using the material sampling method. The water uptake rate is defined as the weight (in grams) of water absorbed per square meter (m ² ) of elastomeric material over the square root of the soaking time (√min). Alternatively, the water absorption rate ranges from about 12 g/m ² /√min to about 100 g/m ² /√min; alternatively from about 25 g/m ² /√min to about 90 g/m ² /√min; alternatively up to approx. 60 g/m ² /√min.

In one aspect, the total water uptake capacity and water uptake rate may depend on the amount of hydrogel material present in the sheet material. The hydrogel material can be characterized as having a water absorbency of 50% to 2000% as measured by the Water Absorbency Test using the Material Sampling Method. In this case, the water absorption capacity of the hydrogel material is determined on the basis of the amount of water absorbed by the hydrogel material in percent by weight of the dry hydrogel material. Alternatively, the water holding capacity of the hydrogel material ranges from about 100% to about 1500%; alternatively in the range of about 300% to about 1200%.

As also discussed above, in some aspects the surface of the sheet material preferably exhibits hydrophilic properties. The hydrophilic properties of the sheet material surface can be characterized by determining the static contact angle of the static sessile droplet on the sheet material surface. Accordingly, in some examples, the surface of the layered material when dry has a static sessile drop contact angle (or dry contact angle) of less than 105° or less than 95°, less than 85° as characterized by the contact angle test. The contact angle test can be performed on a sample obtained by the article sampling method or the coextrusion film sampling method. In some other examples, the layered material has a dry static sessile drop contact angle of from 60° to 100°, from 70° to 100°, or from 65° to 95°.

In other examples, the surface of the sheet material when wet has a static sessile drop contact angle (or wet contact angle) of less than 90°, less than 80°, less than 70°, or less than 60°. In some other examples, the surface has a static sessile droplet contact angle in the range of 45° to 75° when wet. In some cases the contact angle of the dry static stationary droplet contact angle of the surface is greater than the contact angle of the wet static stationary droplet contact angle of the surface by at least 10°, at least 15° or at least 20°, e.g. B. from 10° to 40°, from 10° to 30° or from 10° to 20°.

The surface of the sheet material, including the surface of an article, can also have a low coefficient of friction when the material is wet. Examples of suitable coefficients of friction for the sheet material in a dry state (or coefficient of friction when dry) are less than 1.5, for example in the range from 0.3 to 1.3 or from 0.3 to 0.7, as determined by the coefficient of friction test characterized. The coefficient of friction test can be performed on a sample obtained by the article sampling method or the coextruded film sampling method. Examples of suitable coefficients of friction for the sheet material when wet (or coefficient of friction when wet) are less than 0.8 or less than 0.6, e.g. B. in the range from 0.05 to 0.6, from 0.1 to 0.6 or from 0.3 to 0.5. In addition, the sheet material may exhibit a reduction in its coefficient of friction from dry to wet, e.g. B. a reduction in the range of 15% to 90% or from 50% to 80%. In some cases the coefficient of friction when dry is greater than the coefficient of friction of the material when wet, e.g. B. by a value of at least 0.3 or 0.5 greater, such as. 0.3 to 1.2 or 0.5 to 1.

In addition, the compliance of the sheet material, including an article comprising the material, can be characterized in that it is based on the storage modulus of the sheet material in the dry state (when balanced at 0% relative humidity (RH)) and in a partially wet condition (e.g. when it is equilibrated at 50% RH or at 90% RH) and by reductions in its storage modulus between dry and wet states. In particular, the sheet material can counteract a reduction in storage modulus (ΔE') from the dry state above the wet state. A reduction in storage modulus with increasing water concentration in the hydrogel-containing material corresponds to an increase in compliance since less stress is required at a given strain/strain.

In some aspects, the sheet material exhibits a reduction in storage modulus from its dry state to its wet state (50% RH) of greater than 20%, greater than 40%, greater than 60%, greater than 75%, greater than 90%, or greater as 99% relative to the storage modulus when dry and as characterized by the storage modulus test using the clean film sampling method.

In some other aspects, the dry storage modulus of the sheet material is greater than 25 megapascals (MPa), greater than 50 MPa, greater than 100 MPa, greater than 300 MPa greater than its wet storage modulus (50% RH). F.), or by more than 500 MPa, for example from 25 MPa to 800 MPa, from 50 MPa to 800 MPa, from 100 MPa to 800 MPa, from 200 MPa to 800 MPa, from 400 MPa to 800 MPa, from 25 MPa to 200 MPa, from 25 MPa to 100 MPa or from 50 MPa to 200 MPa. In addition, the storage modulus in the dry state can range from 40 MPa to 800 MPa, from 100 MPa to 600 MPa, or from 200 MPa to 400 MPa as characterized by the storage modulus test. Additionally, the wet storage modulus can range from 0.003 MPa to 100 MPa, from 1 MPa to 60 MPa, or from 20 MPa to 40 MPa.

In other aspects, the sheet material exhibits a reduction in storage modulus from its dry state to its wet state (90% RH) of greater than 20%, greater than 40%, greater than 60%, greater than 75%, greater than 90%, or greater as 99% relative to the storage modulus when dry and as characterized by the storage modulus test using the clean film sampling method. In other aspects, the dry storage modulus of the sheet material is greater than the dry storage modulus (90% RH) by more than 25 megapascals (MPa), by more than 50 MPa, by more than 100 MPa, by more than 300 MPa, or by more than 500 MPa, for example in the range from 25 MPa to 800 MPa, from 50 MPa to 800 MPa, from 100 MPa to 800 MPa, from 200 MPa to 800 MPa, from 400 MPa to 800 MPa, from 25 MPa to 200 MPa MPa, from 25 MPa to 100 MPa or from 50 MPa to 200 MPa. In addition, the storage modulus in the dry state can range from 40 MPa to 800 MPa, from 100 MPa to 600 MPa, or from 200 MPa to 400 MPa as characterized by the storage modulus test. Additionally, the wet storage modulus can range from 0.003 MPa to 100 MPa, from 1 MPa to 60 MPa, or from 20 MPa to 40 MPa.

In addition to a reduction in storage modulus, the sheet material may also exhibit a reduction in its glass transition temperature from the dry state (when equilibrated at 0% relative humidity (RH)) to the wet state (when equilibrated at 90% RH). Without wishing to be bound by theory, it is believed that the water absorbed by the sheet material plasticizes the sheet material, reducing its storage modulus and glass transition temperature, making the sheet material more compliant (e.g., compressible, expandable, and stretchable).

In some aspects, the layered material can exhibit a reduction in glass transition temperature (ΔTg) from its dry glass transition temperature (0% RH) to its wet glass transition temperature (90% RH) by more than 5 °C, more than 6 °C, more than 10 °C or greater than 15 °C as characterized by the glass transition temperature test using the clean film sampling method or the clean material sampling method. For example, reducing the glass transition temperature (ΔT _g ) from more than 5 °C difference up to 40 °C difference, from more than 6 °C difference up to 50 °C difference, from more than 10 -°C differential up to 30°C differential, from more than 30°C differential to 45°C differential, or from 15°C differential to 20°C differential. The layered material may also have a dry glass transition temperature in the range from -40°C to -80°C or from -40°C to -60°C.

Alternatively (or in addition), reducing the glass transition temperature (ΔT _g ) from 5 °C differential to 40 °C differential, from 10 °C differential to 30 °C differential, or from 15 °C differential difference up to 20 °C difference. The layered material may also have a dry glass transition temperature in the range from -40°C to -80°C or from -40°C to -60°C.

The total amount of water that the layered material can absorb depends on a number of factors, such as e.g. B. its composition (z. B. its hydrophilicity), its crosslink density, its thickness and the like. The water absorption capacity and the water absorption rate of the layered material depend on the size and shape of its geometry and are usually based on the same facts ren. Conversely, the water uptake rate is transient and can be defined kinetically. The three main factors affecting the water absorption rate of layered material for a given part geometry are time, thickness, and the exposed surface area available for water absorption.

Even if the layer material can swell during water absorption and transitions between the different material states with corresponding thicknesses, the saturation thickness of the layer material preferably remains smaller than the length of the traction element. This choice of layer material and the corresponding dry and saturated thicknesses ensure that the traction elements can continue to provide ground-contacting traction during use of the footwear even when the layer material is in a fully swollen state. For example, the average distance between the lengths of the traction elements and the saturation thickness of the sheet material is desirably at least 8 millimeters. For example, the average distance can be at least 9 millimeters, 10 millimeters or more.

As also mentioned above, in addition to swelling, the sheet material's compliance can also change from relatively stiff (i.e., when dry) to increasingly more extensible, compressible, and malleable (i.e., when wet). The increased resilience can thus result in the sheet material compressing easily under an applied pressure (e.g., foot impact with the ground) and, in some aspects, quickly recovering at least some of the retained water (depending on the amount of compression). emits. Without wishing to be bound by theory, it is believed that this compressive compliance alone, water ejection alone, or both in combination can disrupt subsurface adhesion and/or cohesion, preventing or otherwise reducing subsurface accumulation.

In addition to rapidly shedding water, in particular examples, the compressed sheet material is capable of rapidly reabsorbing water when the compression is released (e.g., lifting from a footstep in normal use). Thus, during use in a wet or damp environment (e.g., muddy or wet ground), the layered material can dynamically expel water upon successive foot strikes and repeatedly absorb water, particularly from a wet surface. In this way, the layer material can also prevent underground accumulation over longer periods of time (e.g. during an entire competition), especially if groundwater is available for re-absorption.

The sheet material is not only effective in preventing ground build-up, but has also proven to be sufficiently durable for the intended use on the ground-contacting side of the footwear. In various aspects, the useful life of the layered material (and shoes incorporating it) is at least 10 hours, 20 hours, 50 hours, 100 hours, 120 hours, or 150 hours of wear.

As used herein, the terms "ingest," "receptive," "incorporates," "incorporate," and the like refer to the wicking of a liquid (e.g., water) from an external source into the sheet material, e.g. B. by absorption, adsorption or both. Additionally, as briefly mentioned above, the term "water" refers to an aqueous liquid that can be pure water or an aqueous vehicle with minor amounts of dissolved, dispersed, or otherwise suspended matter (e.g., particles, other liquids, and the like). can.

As described herein, the outward facing layer includes the first material. In one aspect, the first material is a hydrogel material. The hydrogel material can be a polymeric hydrogel. In another aspect, the polymeric hydrogel may include or consist essentially of a polyurethane hydrogel. Polyurethane hydrogels are made from one or more diisocyanate(s) and one or more hydrophilic diol(s). In addition to the hydrophilic diol, the polymer can also contain a hydrophobic diol. The polymerisation is normally carried out using an approximately equivalent amount of the diol and diisocyanate. Examples of hydrophilic diols are polyethylene glycols or copolymers of ethylene glycol and propylene glycol. The diisocyanate can be selected from a variety of aliphatic or aromatic diisocyanates. The hydrophobicity of the resulting polymer is determined by the amount and type of hydrophilic diols, the type and amount of hydrophobic diols, and the type and amount of diisocyanates. More details about polyurethane are listed here.

In another aspect, the polymeric hydrogel may contain or consist essentially of a polyurea hydrogel. Polyurea hydrogels are made from one or more diisocyanate(s) and one or more hydrophilic diamine(s). In addition to the hydrophilic diamines, the polymer can also contain a hydrophobic diamine. The polymerisation is normally carried out using an approximately equivalent amount of the diamine and diisocyanate. Typical hydrophilic diamines are amine-terminated polyethylene oxides and amine-terminated polyethylene oxide/polypropylene copolymers. Examples include Jeffamine® diamines sold by Huntsman (The Woodlands, TX, USA). The diisocyanate can be selected from a variety of aliphatic or aromatic diisocyanates. The hydrophobicity of the resulting polymer is determined by the amount and type of hydrophilic diamines, the type and amount of hydrophobic diamines, and the type and amount of diisocyanates. More details about polyurea are listed here.

In another aspect, the polymeric hydrogel may include a polyester hydrogel or consist essentially of a polyurea hydrogel. Polyester hydrogels can be prepared from dicarboxylic acids (or dicarboxylic acid derivatives) and diols, all or part of the diol being a hydrophilic diol. Examples of hydrophilic diols are polyethylene glycols or copolymers of ethylene glycol and propylene glycol. A second hydrophobic diol can also be used to control the polarity of the final polymer. One or more diacids can be used, which can be either aromatic or aliphatic. Of particular interest are block polyesters made from hydrophilic diols and lactones of hydroxy acids. The lactone is polymerized at both ends of the hydrophilic diol to produce a triblock polymer. In addition, these triblock segments can be linked together to produce a multiblock polymer by reaction with a dicarboxylic acid. More details about polyurea are listed here.

In another aspect, the polymeric hydrogel may contain or consist essentially of a polycarbonate hydrogel. Polycarbonates are typically made by reacting a diol with phosgene or a carbonate diester. A hydrophilic polycarbonate is produced when some or all of the diol is a hydrophilic diol. Examples of hydrophilic diols are hydroxyl-terminated polyethers of ethylene glycol or polyethers of ethylene glycol with propylene glycol. A second hydrophobic diol can also be included to control the polarity of the final polymer. More details about polycarbonate are listed here.

In one embodiment, the polymeric hydrogel may contain or consist essentially of a polyetheramide hydrogel. Polyetheramides are made from dicarboxylic acids (or dicarboxylic acid derivatives) and polyetherdiamines (a polyether terminated with an amino group at each end). Polyethers with hydrophilic amine end groups produce hydrophilic polymers that swell with water. Hydrophobic diamines can be used in conjunction with hydrophilic diamines to control the hydrophilicity of the final polymer. In addition, the type of dicarboxylic acid segment can be chosen to control the polarity of the polymer and the physical properties of the polymer. Typical hydrophilic diamines are amine-terminated polyethylene oxides and amine-terminated polyethylene oxide/polypropylene copolymers. Examples include Jeffamine® diamines sold by Huntsman (The Woodlands, TX, USA). More details on polyetheramides are given here.

In one aspect, the polymeric hydrogel may comprise, or consist essentially of, a hydrogel formed from addition polymers of ethylenically unsaturated monomers. The addition polymers of ethylenically unsaturated monomers can be any polymer. Polymers prepared by the free radical polymerization of one or more hydrophilic ethylenically unsaturated monomers and one or more hydrophobic ethylenically unsaturated monomers. Examples of hydrophilic monomers are acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, sodium p-styrenesulfonate, [3-(methacryloylamino)propyl]trimethylammonium chloride, 2-hydroxyethyl methacrylate, acrylamide, N,N-dimethylacrylamide, 2-vinylpyrrolidone , (meth)acrylate ester of polyethylene glycol and (meth)acrylate ester of polyethylene glycol monomethyl ether. Examples of hydrophobic monomers are (meth)acrylate esters of C1 to C4 alcohols, polystyrene, polystyrene methacrylate macromonomer, and mono(meth)acrylate esters of siloxanes. Both water absorption and physical properties are tuned by the choice of monomer and the amounts of each type of monomer. Further details on ethylenically unsaturated monomers are given here.

The addition polymers made from ethylenically unsaturated monomers can be comb polymers. Comb polymers are produced when one of the monomers is a macromer (an oligomer with an ethylenically unsaturated group at one end). In one case, the main chain is hydrophilic while the side chain are hydrophobic. Alternatively, the comb backbone can be hydrophobic while the side chains are hydrophilic. An example is a backbone of a hydrophobic monomer such as styrene with the methacrylate monoester of polyethylene glycol.

The addition polymers made from ethylenically unsaturated monomers can be block polymers. Block polymers of ethylenically unsaturated monomers can be prepared by methods such as anionic polymerization or controlled free radical polymerization. Hydrogels are made when the polymer has both hydrophilic blocks and hydrophobic blocks. The polymer can be a diblock polymer (A-B), triblock polymer (A-B-A), or multiblock polymer. Triblock polymers with hydrophobic endblocks and a hydrophilic midblock are most useful for this application. Block polymers can also be made by other means. Partial hydrolysis of polyacrylonitrile polymers produces multiblock polymers with hydrophilic domains (hydrolyzed) separated by hydrophobic domains (non-hydrolyzed) such that the partially hydrolyzed polymer acts as a hydrogel. Upon hydrolysis, acrylonitrile units are converted into hydrophilic acrylamide or acrylic acid units in a multiblock pattern.

The polymeric hydrogel may include, or consist essentially of, a hydrogel formed from copolymers. Copolymers combine two or more types of polymers within each polymer chain to achieve desired properties. Of particular interest are polyurethane/polyurea copolymers, polyurethane/polyester copolymers, polyester/polycarbonate copolymers.

Having described aspects of the hydrogel material, the elastomeric material, the thermoplastic hot melt adhesive and the adhesive layer, further details of the thermoplastic polymer are now provided. In some aspects, a thermoplastic polymer can include polymers of the same or different types of monomers (e.g., homopolymers and copolymers, including terpolymers). In certain aspects, the thermoplastic polymer can contain various monomers that are randomly distributed in the polymer (e.g., a random copolymer). The term "polymer" refers to a polymerized molecule having one or more types of monomers, which may be the same or different. When the monomer types are the same, the polymer can be called a homopolymer, and when the monomers are different, the polymer can be called a copolymer. The term "copolymer" is a polymer having two or more types of monomer types and includes terpolymers (i.e., copolymers having three types of monomers). In one aspect, the "monomer" can include various functional groups or segments, but for convenience it is generally referred to as a monomer.

For example, the thermoplastic polymer can be a polymer that has repeating polymer units of the same chemical structure (segments) that are relatively harder (hard segments) and repeating polymer segments that are relatively softer (soft segments). In various aspects, the polymer has repeating hard segments and soft segments, physical connections may be within the segments or between the segments, or both within and between the segments. Particular examples of hard segments are isocyanate segments. Specific examples of soft segments are an alkoxy group such as polyether segments and polyester segments. As used herein, the polymeric segment can be referred to as a particular type of polymeric segment, such as e.g. e.g., an isocyanate segment (e.g., a diisocyanate segment), an alcoholic polyamide segment (e.g., a polyether segment, a polyester segment), and the like. It is understood that the chemical structure of the segment is derived from the chemical structure described. For example, an isocyanate segment is a polymerized entity having an isocyanate functional group. When referring to polymer segments of a particular chemical structure, the polymer may contain up to 10 mole percent of segments of other chemical structures. For example, as used herein, a polyether segment means up to 10 mole percent non-polyether segments.

In certain aspects, the thermoplastic polymer can be a thermoplastic polyurethane (also referred to as "TPU"). In aspects, the thermoplastic polyurethane can be a thermoplastic polyurethane polymer. In such aspects, the thermoplastic polyurethane polymer can include hard and soft segments. In aspects, the hard segments may contain or consist of isocyanate segments (e.g., diisocyanate segments). In the same or alternative aspects, the soft segments can include or consist of alkoxy segments (e.g., polyether segments or polyester segments or a combination of polyether segments and polyester segments). In a particular aspect, the thermoplastic material may comprise, or consist essentially of, an elastomeric thermoplastic polyurethane having repeating hard segments and repeating soft segments.

thermoplastic polyurethanes

In aspects, one or more of the thermoplastic polyurethanes can be prepared by polymerizing one or more isocyanates with one or more polyols to produce polymer chains having carbamate linkages (-N(CO)O-) as shown in Formula 1 below, wherein the / the isocyanate (s) each preferably contain two or more isocyanate groups (-NCO) per molecule, such as. B. 2, 3 or 4 isocyanate groups per molecule (whereby, however, monofunctional isocyanates can optionally also be present, e.g. as chain-terminating units).

In these embodiments, each R ¹ and R ₂ is independently an aliphatic or aromatic segment. Optionally, each R ₂ can be a hydrophilic segment.

Additionally, the isocyanates can also be chain extended with one or more chain extenders to bridge two or more isocyanates. This can produce polyurethane polymer chains as shown below in Formula 2 where R ₃ includes the chain extender. As with each of R ₁ and R _{3 ,} each R ₃ is independently an aliphatic or aromatic segment.

Each R ₁ segment or the first segment in formulas 1 and 2 may independently contain a linear or branched C _3-30 segment based on the particular isocyanate(s) used and may be aliphatic, aromatic or a Combination of aliphatic and aromatic components included. The term "aliphatic" refers to a saturated or unsaturated organic molecule that does not contain a cyclic conjugated ring system with delocalized pi electrons. In comparison, the term “aromatic” refers to a cyclic conjugated ring system with delocalized pi electrons with greater stability than a hypothetical ring system with localized pi electrons.

Each R ₁ segment may be present in an amount of from 5% to 85%, from 5% to 70%, or from 10% to 50% by weight, based on the total weight of reactant monomers.

In aliphatic (aliphatic isocyanate(s)) embodiments, each R ₁ segment may contain a linear aliphatic group, a branched aliphatic group, a cycloaliphatic group, or combinations thereof. For example, each R ₁ segment can be a linear or branched C _3-20 alkylene segment (e.g. C _4-15 alkylene or C _6-10 alkylene), one or more C _3-8 cycloalkylene segments (e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl) and combinations thereof.

Examples of suitable aliphatic diisocyanates for preparing the polyurethane polymer chains are hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), butylene diisocyanate (BDI), bisisocyanatocyclohexylmethane (HMDI), 2,2,4-trimethylhexamethylene diisocyanate (T _m DI), bisisocyanatomethylcyclohexane, bisisocyanatomethyltricyclodecane, norbornane diisocyanate (NDI), cyclohexane diisocyanate (CHDI), 4,4'-dicyclohexylmethane diisocyanate (H12MDI), diisocyanatododecane, lysine diisocyanate, and combinations thereof.

In one aspect, the diisocyanate segments can contain aliphatic diisocyanate segments. In one aspect, the majority of the diisocyanate segments comprise the aliphatic diisocyanate segments. In one aspect, at least 90% of the diisocyanate segments are aliphatic diisocyanate segments. In one aspect, the diisocyanate segments consist essentially of aliphatic diisocyanate segments. In one aspect, the aliphatic diisocyanate segments are essentially (e.g., about 50% or more, about 60% or more, about 70% or more, about 80% or more, about 90% or more) linear aliphatic diisocyanate segments. In one aspect, at least 80% of the aliphatic diisocyanate segments are aliphatic diisocyanate segments that are free of side chains. In one aspect, the aliphatic diisocyanate segments comprise C ₂ -C ₁₀ linear aliphatic diisocyanate segments.

In aromatic embodiments (from aromatic isocyanate(s)), each R ₁ segment may contain one or more aromatic groups, such as e.g. phenyl, naphthyl, tetrahydronaphthyl, phenanthrenyl, biphenylenyl, indanyl, indenyl, indenyl, anthracenyl and fluorenyl. Unless otherwise specified, an aromatic group can be an unsubstituted aromatic group or a substituted aromatic group and also includes heteroaromatic groups. "Heteroaromatic" refers to monocyclic or polycyclic (e.g. fused bicyclic and fused tricyclic) aromatic ring systems in which one to four ring atoms are selected from oxygen, nitrogen or sulfur and the remaining ring atoms are carbon and in which the ring system is terminated by a of the ring atoms is connected to the rest of the molecule. Examples of suitable heteroaryl groups are pyridyl, pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl, tetrazolyl, oxazolyl, isooxazolyl, thiadiazolyl, oxadiazolyl, furanyl, quinolinyl, isoquinolinyl, benzoxazolyl, benzimidazolyl and benzothiazolyl.

Examples of suitable aromatic diisocyanates for preparing the polyurethane polymer chains are toluene diisocyanate (TDI), TDI adducts with trimethyloylpropane (T _m P), methylene diphenyl diisocyanate (MDI), xylene diisocyanate (XDI), tetramethylxylylene diisocyanate (T _m XDI), hydrogenated xylene diisocyanate (HXDI) , naphthalene-1,5-diisocyanate (NDI), 1,5-tetrahydronaphthalene diisocyanate, para-phenylene diisocyanate (PPDI), 3,3'-dimethyldiphenyl1-4,4'-diisocyanate (DDDI), 4,4'-dibenzyl diisocyanate (DBDI ), 4-chloro-1,3-phenylene diisocyanate and combinations thereof. In some embodiments, the polymer chains are essentially free of aromatic groups.

In certain aspects, the polyurethane polymer chains are made from diisocyanates including HMDI, TDI, MDI, H ₁₂ -aliphatics, and combinations thereof. For example, the low processing temperature polymeric composition of the present disclosure may comprise one or more polyurethane polymer chains made from diisocyanates including HMDI, TDI, MDI, H ₁₂ -aliphatics, and combinations thereof.

In certain aspects, polyurethane chains that are crosslinked (e.g., partially crosslinked polyurethane polymers that retain their thermoplastic properties) or that can be crosslinked can be used consistent with the present disclosure. Using multifunctional isocyanates it is possible to produce crosslinked or crosslinkable polyurethane polymer chains. Examples of suitable triisocyanates for making the polyurethane polymer chains are TDI, HDI, and IPDI adducts with trimethyloylpropane (T _m P), uretdiones (ie, dimerized isocyanates), polymeric MDI, and combinations thereof.

The R ₃ segment in formula 2 may contain a linear or branched C ₂ -C ₁₀ segment based on the particular chain extender polyol used, and it may e.g. Example, be aliphatic, aromatic or a polyether. Examples of suitable chain extender polyols for preparing the polyurethane polymer chains are ethylene glycol, ethylene glycol lower oligomers (e.g., diethylene glycol, triethylene glycol, and tetraethylene glycol), 1,2-propylene glycol, 1,3-propylene glycol, propylene glycol lower oligomers (e.g., dipropylene glycol, tripropylene glycol and tetrapropylene glycol), 1,4-butylene glycol, 2,3-butylene glycol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 2-ethyl-1,6-hexanediol, 1 -Methyl-1,3-propanediol, 2-methyl-1,3-propanediol, dihydroxyalkylated aromatic compounds (e.g. bis(2-hydroxyethyl)ether of hydroquinone and resorcinol, xylene-a,a-diols, bis(2 -Hydroxyethyl) ethers of xylene-a,a-diols and combinations thereof.

The R ₂ segment in formulas 1 and 2 may contain a polyether group, a polyester group, a polycarbonate group, an aliphatic group or an aromatic group. Each R ₂ segment may be present in an amount of from 5% to 85%, from 5% to 70%, or from 10% to 50% by weight, based on the total weight of reactant monomers.

In some examples, at least one R ₂ segment of the thermoplastic polyurethane contains a polyether segment (ie, a segment having one or more ether groups). Suitable polyethers include but are not limited to polyethylene oxide (PEO), polypropylene oxide (PPO), polytetrahydrofuran (PTHF), polytetramethylene oxide (PT _m O), and combinations thereof. The term "alkyl" as used herein refers to straight and branched chain saturated hydrocarbon groups containing one to thirty carbon atoms, for example one to twenty carbon atoms or one to ten carbon atoms. The term C _n means that the alkyl group has "n" carbon atoms. For example, C ₄ alkyl refers to an alkyl group that has 4 carbon atoms. C _1-7 alkyl refers to an alkyl group having a number of carbon atoms covering the entire range (i.e. 1 to 7 carbon atoms) plus all subgroups (e.g. 1-6, 2-7, 1-5, 3- 6, 1, 2, 3, 4, 5, 6 and 7 carbon atoms). Non-limiting examples of alkyl groups are methyl, ethyl, n -propyl, isopropyl, n -butyl, sec -butyl (2-methylpropyl), t -butyl (1,1-dimethylethyl), 3,3-dimethylpentyl, and 2-ethylhexyl . Unless otherwise specified, an alkyl group can be an unsubstituted alkyl group or a substituted alkyl group.

In some examples of the thermoplastic polyurethane, the at least one R ₂ segment comprises a polyester segment. The polyester segment can be derived from the polyesterification of one or more dihydric alcohols (eg, ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,3-butanediol, 2-methylpentanediol-1, 5,diethylene glycol, 1,5-pentanediol, 1,5-hexanediol, 1,2-dodecanediol, cyclohexanedimethanol, and combinations thereof) with one or more dicarboxylic acids (e.g., adipic acid, succinic acid, sebacic acid, suberic acid, methyladipic acid, glutaric acid, pimelic acid , azelaic acid, thiodipropionic acid and citraconic acid and combinations thereof). The polyester can also be derived from polycarbonate prepolymers such as poly(hexamethylene carbonate) glycol, poly(propylene carbonate) glycol, poly(tetramethylene carbonate) glycol and poly(nonanemethylene carbonate) glycol. Suitable polyesters can e.g. B. polyethylene adipate (PEA), poly (1,4-butylene adipate), poly (tetramethylene adipate), poly (hexamethylene adipate), polycaprolactone, polyhexamethylene carbonate, poly (propylene carbonate), poly (tetramethylene carbonate), poly (nonanemethylene carbonate) and combinations thereof.

In various of the thermoplastic polyurethanes, at least one R ₂ segment includes a polycarbonate segment. The polycarbonate segment may be formed from the reaction of one or more dihydric glycols (e.g., ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,3-butanediol, 2-methylpentanediol-1 ,5-diethylene glycol, 1,5-pentanediol, 1,5-hexanediol, 1,2-dodecanediol, cyclohexanedimethanol, and combinations thereof) can be derivatized with ethylene carbonate.

In various examples, the aliphatic group is linear and can be, for example, a C _1-20 alkylene chain or a C _1-20 alkenylene chain (e.g. methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene , undecylene, dodecylene, tridecylene, ethenylene, propenylene, butenylene, pentenylene, hexenylene, heptenylene, octenylene, nonenylene, decenylene, undecenylene, dodecenylene, tridecenylene). The term "alkylene" denotes a divalent hydrocarbon. The term C _n means that the alkylene group has "n" carbon atoms. For example, C _1-6 alkylene denotes an alkylene group, e.g. B. 1, 2, 3, 4, 5, or 6 carbon atoms. The term "alkenylene" refers to a divalent hydrocarbon that has at least one double bond.

In various aspects, the aliphatic and aromatic groups can be substituted with one or more relatively hydrophilic and/or charged side groups. In some aspects the hydrophilic side group includes one or more (e.g. 2, 3, 4, 5, 6, 7, 8, 9, 10 or more) hydroxyl groups. In various aspects, the pendant hydrophilic group includes one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10 or more) amino groups. In some cases, the pendant hydrophilic group includes one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10 or more) carboxyl groups. For example, the aliphatic group can include one or more polyacrylic acid groups. In some cases, the pendant hydrophilic group can include one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10 or more) sulfonate groups. In some cases, the pendant hydrophilic group includes one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10 or more) phosphate groups. In some examples, the pendant hydrophilic group includes one or more ammonium groups (e.g., tertiary and/or quaternary ammonium). In other examples, the pendant hydrophilic group includes one or more zwitterionic groups (e.g., a betaine such as poly(carboxybetaine (pCB)) and ammonium phosphonate groups such as a phosphatidylcholine group).

In some aspects, the R ₂ segment can include charged groups capable of binding to a counterion to ionically crosslink the thermoplastic polymer and form ionomers. In these aspects, R ₂ is, for example, an aliphatic or aromatic group having pendant amino, carboxyl, sulfonate, phosphate, ammonium, or zwitterionic groups, or combinations thereof.

In various cases when a pendant hydrophilic group is present, the pendant "hydrophilic" group is at least one polyether group, e.g. B. two polyether groups. In other cases, the pendant hydrophilic group is at least one polyester. In various cases the hydrophilic side group is a polylactone group (e.g. polyvinylpyrrolidone). Each carbon atom of the hydrophilic side group can optionally be substituted with e.g. B. a C _1-6 alkyl group can be substituted. In some of these aspects, the aliphatic and aromatic groups can be graft polymeric groups with the pendant groups being homopolymeric groups (e.g., polyether groups, polyester groups, polyvinylpyrrolidone groups).

In some aspects, the pendant hydrophilic group is a polyether group (e.g., a polyethylene oxide group, a polyethylene glycol group), a polyvinylpyrrolidone group, a polyacrylic acid group, or combinations thereof.

The hydrophilic side group can be attached to the aliphatic group or the aromatic group through a linker. The linker can be any bifunctional small molecule (e.g. C _1-20 ) capable of connecting the hydrophilic side group to the aliphatic or aromatic group. For example, the linker can include a diisocyanate group, as previously described herein, which when joined to the hydrophilic side group and the aliphatic or aromatic group forms a carbamate linkage. In some aspects, the linker can be 4,4'-diphenylmethane diisocyanate (MDI), as shown below.

In some exemplary aspects, the pendant hydrophilic group is a polyethylene oxide group and the linking group is MDI, as shown below.

In some cases, the hydrophilic side group is functionalized to enable it to be attached to the aliphatic or aromatic group, optionally through the linker. For example, in various aspects when the pendant hydrophilic group includes an alkene group that involves a Michael addition a sulfhydryl-containing bifunctional molecule (ie, with a molecule having a second reactive group, such as a hydroxyl group or amino group) to yield a hydrophilic group that can react with the polymer backbone, optionally through the linker, using the second reactive group. For example, when the pendant hydrophilic group is a polyvinylpyrrolidone group, it can react with the sulfhydryl group on mercaptoethanol to give hydroxyl-functionalized polyvinylpyrrolidone, as shown below.

In some of the aspects disclosed herein, at least one R ₂ segment includes a polytetramethylene oxide group. In other exemplary aspects, at least one R ₂ segment may include an aliphatic polyol group that has been functionalized with a polyethylene oxide group or a polyvinylpyrrolidone group, e.g. B. the polyols described in EP Patent No. 2,462,908. For example, the R ₂ segment can be derived from the reaction product of a polyol (e.g., pentaerythritol or 2,2,3-trihydroxypropanol) and either MDI-derivatized methoxypolyethylene glycol (to yield compounds as shown in Formulas 6 and 7) or from MDI-derivatized polyvinylpyrrolidone (to obtain compounds as shown in formulas 8 and 9) previously reacted with mercaptoethanol, as shown below.

wobei a 1 bis 10 oder größer ist (z. B. 1, 2, 3, 4, 5, 6, 7, 8, 9, oder 10); jedes R₄ unabhängig voneinander Wasserstoff, C_1-18-Alkyl, C_2-18-Alkenyl, Aryl, oder Polyether ist; und jedes R₅ unabhängig voneinander C_1-10-Alkylen, Polyether, oder Polyurethan ist.In various cases, at least one R ₂ is a polysiloxane. In these cases, R ₂ can be derivatized from a silicone monomer of Formula 10, such as a silicone monomer that is im US Pat. No. 5,969,076 is disclosed, which is hereby incorporated herein by reference:

where a is 1 to 10 or greater (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10); each R ₄ is independently hydrogen, C _1-18 alkyl, C _2-18 alkenyl, aryl, or polyether; and each R ₅ is independently C _1-10 alkylene, polyether, or polyurethane.

In some aspects, each R ₄ is independently an H, C _1-10 alkyl, C _2-10 alkenyl, C _1-6 aryl, polyethylene, polypropylene, or polybutylene group. For example, each R ₄ can be independently selected from the group consisting of methyl, ethyl, n -propyl, isopropyl, n -butyl, isobutyl, s -butyl, t -butyl, ethenyl, propenyl, phenyl and polyethylene groups.

In various aspects, each R ₅ independently includes a C _1-10 alkylene group (eg, methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, or decylene group). In other cases, each R ⁵ is a polyether group (e.g., a polyethylene, polypropylene, or polybutylene group). In various cases, each R5 is a polyurethane group.

wobei die Variablen wie oben beschrieben sind. Zusätzlich können die Isocyanate auch mit einer oder mehreren Polyamino- oder Polythiol-Kettenverlängerern verlängert werden, um zwei oder mehrere Isocyanate zu überbrücken, wie zuvor für die Polyurethane aus Formel 2 beschrieben.Optionally, in some aspects, the polyurethane can include an at least partially crosslinked polymeric network that includes polymer chains that are derivatives of polyurethane. In such cases, it is understood that the degree of crosslinking is such that the polyurethane retains thermoplastic properties (ie, the crosslinked thermoplastic polyurethane can be softened or melted and rehardened under the process conditions described herein). The crosslinked polymeric network can be prepared by polymerizing one or more isocyanates with one or more polyamine compounds, polysulfhydryl compounds, or combinations thereof, as shown below in Formulas 11 and 12:

where the variables are as described above. Additionally, the isocyanates can also be extended with one or more polyamino or polythiol chain extenders to bridge two or more isocyanates, as previously described for the polyurethanes of Formula 2.

As described herein, the thermoplastic polyurethane can be physically modified by e.g. B. non-polar or polar interactions between the urethane or carbamate groups on the polymers are crosslinked (the hard segments). In these aspects, component R ₁ in Formula 1 and components R ₁ and R ₃ in Formula 2 form that portion of the polymer that is often referred to as the "hard segment" and component R ₂ forms that portion of the polymer that often referred to as the "soft segment". In these aspects, the soft segment can be covalently attached to the hard segment. In some examples, the thermoplastic polyurethane having physically crosslinked hard and soft segments can be a hydrophilic thermoplastic polyurethane (ie, a thermoplastic polyurethane that includes hydrophilic groups as disclosed herein).

Thermoplastic polyamide

In various aspects, the thermoplastic polymer can include a thermoplastic polyamide. The thermoplastic polyamide can be a polyamide homopolymer having repeating polyamide segments of the same chemical structure. Alternatively, the polyamide may comprise a series of polyamide segments that have different chemical structures (e.g., polyamide 6 segments, polyamide 11 segments, polyamide 12 segments, polyamide 66 segments, etc.). The polyamide segments, which have different chemical structures, can be arranged randomly or they can be arranged as repeating blocks.

In aspects, the thermoplastic polymers can be a block copolyamide. For example, the block copolyamide can have repeating hard segments and repeating soft segments. The hard segments can include polyamide segments and the soft segments can be non-polyamide segments. The thermoplastic polymers can be an elastomeric thermoplastic copolyamide, which includes or consists of block copolyamides having repeating hard segments and repeating soft segments. In block copolymers, including block copolymers having repeating hard segments and soft segments, physical crosslinks may be present within segments or between segments or both within and between segments.

The thermoplastic polyamide can be a copolyamide (i.e., a copolymer that includes polyamide segments and non-polyamide segments). The polyamide segments of the copolyamide may comprise or consist of polyamide 6 segments, polyamide 11 segments, polyamide 12 segments, polyamide 66 segments or a combination thereof. The polyamide segments of the copolyamide can be randomly arranged or they can be arranged as repeating segments. In a particular example, the polyamide segments may include or consist of polyamide 6 segments, or polyamide 12 segments, or both polyamide 6 segments and polyamide 12 segments. In the example where the polyamide segments of the copolyamide include polyamide 6 segments and polyamide 12 segments, the segments may be randomly arranged. The non-polyamide segments of the copolyamide can include polyether segments, polyester segments, or both polyether segments and polyester segments. The copolyamide can be a copolyamide or it can be a random copolyamide. The thermoplastic copolyamide can be formed from the polycondensation of a polyamide oligomer or prepolymer with a second oligomer prepolymer to form a copolyamide (i.e., a copolymer that includes polyamide segments). Optionally, the second prepolymer can be a hydrophilic prepolymer.

In some aspects, the thermoplastic polyamide itself, or the polyamide segment of the thermoplastic copolyamide, can be derivatized from the condensation of polyamide prepolymers, such as lactams, amino acids and/or diamino compounds with dicarboxylic acids, or activated forms thereof. The resulting polyamide segments include amide linkages (-(CO)NH-). The term "amino acid" refers to a molecule that has at least one amino group and at least one carboxyl group. Each polyamide segment of the thermoplastic polyamide may be the same or different.

In some aspects, the thermoplastic polyamide or the polyamide segment of the thermoplastic copolyamide is derived from the polycondensation of lactams and/or amino acids and includes an amide segment having a structure shown in Formula 13 below, where R ₆ is the segment of the polyamide, derived from the lactam or amino acid.

In some aspects, R ₆ is derivatized from a lactam. In some cases, R ₆ is derivatized from a C _3-20 lactam, or a C _4-15 lactam, or a C _6-12 lactam. For example, R ₆ can be derivatized from caprolactam or laurolactam. In some cases, R ₆ is derivatized from one or more amino acids. In various cases, R ₆ is derivatized from a C _4-25 amino acid or a C _5-20 amino acid or a C _8-5 amino acid. For example, R ₆ can be derivatized from 12-aminolauric acid or 11-aminoundecanoic acid.

wobei m 3-20 ist und n 1-8 ist. In einigen beispielhaften Aspekten ist m 4-15 oder 6-12 (z. B. 6, 7, 8, 9, 10, 11, oder 12) und n ist 1, 2, oder 3. Beispielsweise kann m 11 oder 12 sein, und n kann 1 oder 3 sein. In verschiedenen Aspekten wird das thermoplastische Polyamid oder das Polyamidsegment des thermoplastischen Copolyamids aus der Kondensation von Diaminoverbindungen mit Dicarbonsäuren, oder aktivierten Formen davon, derivatisiert und schließt ein Amidsegment ein, das eine Struktur aufweist, die in Formel 15 unten gezeigt wird, wobei R₇ das Segment des Polyamids ist, das aus der Diaminoverbindung derivatisiert wurde, und R₈ das Segment ist, das aus der Dicarbonsäureverbindung derivatisiert wurde:

Optionally, to increase the relative degree of hydrophilicity of the thermoplastic copolyamide, Formula 13 can contain a polyamide-polyether block copolymer segment as shown below:

where m is 3-20 and n is 1-8. In some example aspects, m is 4-15 or 6-12 (e.g., 6, 7, 8, 9, 10, 11, or 12) and n is 1, 2, or 3. For example, m can be 11 or 12 , and n can be 1 or 3. In various aspects, the thermoplastic polyamide or the polyamide segment of the thermoplastic copolyamide is derived from the condensation of diamino compounds with dicarboxylic acids, or activated forms thereof, and includes an amide segment having a structure shown in Formula 15 below, where R ₇ is the segment of the polyamide derivatized from the diamino compound and R ₈ is the segment derivatized from the dicarboxylic acid compound:

In some aspects, R ₇ is derivatized from a diamino compound that includes an aliphatic group having C _4-15 carbon atoms, or C _5-10 carbon atoms, or C _6-9 carbon atoms. In some aspects, the diamino compound includes an aromatic group such as phenyl, naphthyl, xylyl, and tolyl. Suitable diamino compounds from which R ₇ can be derivatized include the following including but not limited to: hexamethylenediamine (HMD), tetramethylenediamine, trimethylhexamethylenediamine (T _m D), m-xylylenediamine (MXD), and 1,5-pentaminediamine. In various aspects, R ₈ is derived from a dicarboxylic acid or an activated form thereof, and includes an aliphatic group having C _4-15 carbon atoms, or C _5-12 carbon atoms, or C _6-10 carbon atoms. In some cases, the dicarboxylic acid or activated form thereof from which R ₈ can be derivatized includes an aromatic group such as phenyl, naphthyl, xylyl and tolyl groups. Suitable carboxylic acids or activated forms thereof from which R ₈ may be derivatized include but are not limited to adipic acid, sebacic acid, terephthalic acid and isophthalic acid. In some aspects, the polymer chains are essentially free of aromatic groups.

In some aspects, each polyamide segment of the thermoplastic polyamide (including the thermoplastic copolyamide) is independently derived from a polyamide prepolymer selected from the group consisting of 12-aminolauric acid, caprolactam, hexamethylenediamine, and adipic acid.

In some aspects, the thermoplastic polyamide comprises or consists of a thermoplastic poly(ether block amide). The thermoplastic poly(ether block amide) can be formed from the polycondensation of a carboxylic acid terminated polyamide prepolymer and a hydroxyl terminated polyether prepolymer to form a thermoplastic poly(ether block amide) as shown in Formula 16:

1. 1) Polyamidblöcke, die Diamin-Kettenenden enthalten, mit Polyoxyalkylenblöcken, die Carbonsäure-Kettenenden enthalten; 2) Polyamidblöcke, die Dicarbon-Kettenenden enthalten, mit Polyoxyalkylenblöcken, die Diamin-Kettenenden enthalten, die durch Cyanoethylierung und Hydrierung aliphatischer dihydroxylierter alpha-omega-Polyoxyalkylene erhalten werden, die als Polyetherdiole bekannt sind; 3) Polyamidblöcke, die Dicarbon-Kettenenden enthalten, mit Polyetherdiolen, wobei die in diesem speziellen Fall erhaltenen Produkte Polyetheresteramide sind. Der Polyamidblock des thermoplastischen Poly(ether-Blockamids) kann von Lactamen, Aminosäuren, und/oder Diaminoverbindungen mit Dicarbonsäuren, wie zuvor beschrieben, derivatisiert werden. Der Polyetherblock kann von einem oder mehreren Polyethern derivatisiert werden, das/die aus der Gruppe ausgewählt ist/sind, die aus Polyethylenoxid (PEO), Polypropylenoxid (PPO), Polytetrahydrofuran (PTHF), Polytetramethylenoxid (PTMO) und Kombinationen daraus besteht.

In various aspects, a disclosed poly(ether-block amide) polymer is made by polycondensation of polyamide blocks containing reactive ends with polyether blocks containing reactive ends. Examples include, but are not limited to:

1. 1) polyamide blocks containing diamine chain ends with polyoxyalkylene blocks containing carboxylic acid chain ends; 2) polyamide blocks containing dicarbon chain ends with polyoxyalkylene blocks containing diamine chain ends obtained by cyanoethylation and hydrogenation of aliphatic dihydroxylated alpha-omega polyoxyalkylenes known as polyether diols; 3) Polyamide blocks containing dicarbon chain ends with polyether diols, the products obtained in this particular case being polyetheresteramides. The polyamide block of the thermoplastic poly(ether-block amide) can be derivatized from lactams, amino acids, and/or diamino compounds with dicarboxylic acids as previously described. The polyether block can be derivatized from one or more polyethers selected from the group consisting of polyethylene oxide (PEO), polypropylene oxide (PPO), polytetrahydrofuran (PTHF), polytetramethylene oxide (PTMO), and combinations thereof.

Poly(ether-block amide) polymers disclosed include those comprising polyamide blocks comprising dicarboxylic chain ends derivatized from the condensation of α,ω-aminocarboxylic acids, of lactams, or of dicarboxylic acids and diamines in the presence of a chain-limiting dicarboxylic acid. In poly(ether block amide) polymers of this type, an α,ω-amino carboxylic acid such as aminoundecanoic acid can be used; a lactam such as caprolactam or lauryl lactam can be used; a dicarboxylic acid such as adipic acid, decanedioic acid or dodecanedioic acid can be used, and a diamine such as hexamethylenediamine can be used; or various combinations of the above. In various aspects, the copolymer comprises polyamide blocks comprising polyamide-12 or polyamide-6.

Poly(ether block amide) polymers disclosed include those comprising polyamide blocks derived from the condensation of one or more α,ω-amino carboxylic acids and/or one or more lactams comprising from 6 to 12 carbon atoms in the presence of a dicarboxylic acid, containing from 4 to 12 carbon atoms, and are of low mass, ie, have an M _n of 400 to 1000. In poly(ether block amide) polymers of this type, an α,ω-amino carboxylic acid such as Ami noundecanoic acid or aminododecanoic acid are used, a dicarboxylic acid such as adipic acid, sebacic acid, isophthalic acid, butanedionic acid, 1,4-cyclohexyldicarboxylic acid, terephthalic acid, the sodium or lithium salt of sulphoisophthalic acid, dimerized fatty acids (these dimerized fatty acids have a dimer content of at least 98% and are preferred hydrogenated) and dodecanedioic acid HOOC-(CH ₂ ) _1O -COOH can be used, and a lactam such as caprolactam and lauryl lactam can be used; or various combinations of the above. In various aspects, the copolymer comprises polyamide blocks derivatized by the condensation of lauryl lactam in the presence of adipic acid or dodecanedioic acid and has a M _n of 750 with a melting point of 127-130°C. In a further aspect, the various components of the polyamide block and their proportions can be chosen so as to obtain a melting point lower than 150°C and advantageously between 90°C and 135°C.

Poly(ether-block amide) polymers disclosed include those comprising polyamide blocks derivatized from the condensation of at least one α,ω-amino carboxylic acid (or a lactam), at least one diamine and at least one dicarboxylic acid. In copolymers of this type, an α,ω-aminocarboxylic acid, the lactam and the dicarboxylic acid can be selected from those described hereinabove, and the diamine, such as an aliphatic diamine comprising from 6 to 12 atoms and which is aryl and/or saturated cycle such as, but not limited to, hexamethylenediamine, piperazine, 1-aminoethylpiperazine, bisaminopropylpiperazine, tetramethylenediamine, octamethylenediamine, decamethylenediamine, dodecamethylenediamine, 1,5-diaminohexane, 2,2,4-trimethyl-1,6- Diaminohexane, diamine polyols, isophoronediamine (IPD), methylpentamethylenediamine (MPDM), bis(aminocyclohexyl)methane (BACM), and bis(3-methyl-4-aminocyclohexyl)methane (BMACM) can be used.

In various aspects, the components of the polyamide block and their proportions can be chosen to obtain a melting point of less than 150°C and advantageously between 90°C and 135°C. In a further aspect, the different components of the polyamide block and their proportions can be chosen in order to obtain a melting point lower than 150°C and advantageously between 90°C and 135°C.

In one aspect, the number average molar mass of the polyamide blocks can be between about 300 g/mol and about 15,000 g/mol, between about 500 g/mol and about 10,000 g/mol, between about 500 g/mol and about 6,000 g/mol, between about 500 g/mol to 5000 g/mol and between about 600 g/mol and about 5000 g/mol. In another aspect, the number average molecular weight of the polyether block can range from about 100 g/mol to about 6000 g/mol, from about 400 g/mol to 3000 g/mol, and from about 200 g/mol to about 3000 g/mol . In yet another aspect, the polyether (PE) content (x) of the poly(ether-block amide) polymer can range from about 0.05 to about 0.8 (i.e., from about 5 mole percent to about 80 mole percent). %). In yet another aspect, the polyether blocks can contain from about 10% to about 50%, from about 20% to about 40%, and from about 30% to about 40% by weight. -% to be available. The polyamide blocks can be present from about 50% to about 90%, from about 60% to about 80%, and from about 70% to about 90% by weight.

In one aspect, the polyether blocks may comprise moieties other than ethylene oxide moieties, such as propylene oxide or polytetrahydrofuran (resulting in polytetramethylene glycol sequences). It is also possible to simultaneously use PEG blocks, ie those composed of ethylene oxide units, PPG blocks, ie those composed of propylene oxide units, and PT _m G blocks, ie those composed of tetramethylene glycol units, also called polytetrahydrofuran . Advantageously, PPG or PT _m G blocks are used. The amount of polyether blocks in the polyamide and polyether blocks containing these copolymers can range from about 10% to about 50% by weight of the copolymer and from about 35% to about 50% by weight.

The copolymers containing polyamide blocks and polyether blocks can be prepared by any means of attaching the polyamide blocks and the polyether blocks. In practice, essentially two processes are used, one being a two-step process and the other being a one-step process.

In the two-step process, the polyamide blocks, which have dicarbon chain ends, are prepared first and then, in a second step, these polyamide blocks are linked to the polyether blocks. The polyamide blocks bearing dicarboxylic chain ends were derivatized by the condensation of polyamide precursors in the presence of a chainstopper dicarboxylic acid. If the polyamide pre When the cursors are only lactams or α,ω-aminocarboxylic acids, a dicarboxylic acid is added. If the precursors already comprise a dicarboxylic acid, this is used in excess with respect to the stoichiometry of the diamines. The reaction usually takes place between 180 and 300°C, preferably 200 to 290°C, and the pressure in the reactor is adjusted to between 5 and 30 bar and maintained for about 2 to 3 hours. The pressure in the reactor is slowly reduced to atmospheric pressure and then the excess water is distilled off, for example for an hour or two.

When the polyamide having carboxylic acid end groups has been prepared, the polyether, polyol and a catalyst are added. The total amount of polyether can be divided up and added in one or more portions, as can the catalyst. In one aspect, the polyether is added first and the reaction of the OH end groups of the polyether and polyol with the COOH end groups of the polyamide begins with the formation of ester linkages and the elimination of water. Water is removed from the reaction mixture as much as possible and then the catalyst is introduced to complete the connection of the polyamide blocks to the polyether blocks. This second stage is carried out with stirring, preferably under a vacuum of at least 50 mbar (5000 Pa) at a temperature at which the reactants and the copolymers obtained are in a molten state. As an example, this temperature can be between 100 and 400°C and usually between 200 and 250°C. The reaction is monitored by measuring the torque exerted on the stirrer by the polymer melt or by measuring the electrical energy consumed by the stirrer. The end of the reaction is determined by the value of the torque or energy targeted. The catalyst is defined as any product that promotes the bonding of the polyamide blocks to the polyether blocks by esterification. Advantageously, the catalyst is a derivative of a metal (M) selected from the group consisting of titanium, zirconium and hafnium. In one aspect, the tetraalkoxide derivative may be prepared in accordance with the general formula M(OR) ₄ , where M represents titanium, zirconium or hafnium and R, which may be the same or different, represents linear or branched alkyl radicals, the 1 to 24 carbon atoms.

In a further aspect the catalyst may comprise a salt of the metal (M), in particular the salt of (M) and an organic acid and the complex salts of the oxide of (M) and/or the hydroxide of (M) and an organic acid. In yet another aspect, the organic acid may be formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, salicylic acid, oxalic acid, malonic acid, succinic acid , glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid and crotonic acid. Acetic and propionic acids are particularly preferred. In some aspects M is zirconium and such salts are called zirconyl salts, e.g. B. the commercial product available under the name zirconyl acetate.

In one aspect, the weight fraction of the catalyst varies from about 0.01 to about 5% of the weight of the mixture of the dicarboxylic polyamide with the polyether diol and the polyol. In a further aspect, the weight fraction of the catalyst varies from about 0.05 to about 2% of the weight of the mixture of the dicarboxylic polyamide with the polyether diol and the polyol.

In the one-step process, the polyamide precursors, the chain stopper and the polyether are mixed together; what is then obtained is a polymer essentially having polyether blocks and polyamide blocks of very different lengths, but also the various reactants that have randomly reacted with each other, that are randomly distributed along the chain. The reactants and catalyst are the same as in the two-step process described above. If the polyamide precursors are only lactams, it is advantageous to add a little water. The copolymer has essentially the same polyether blocks and the same polyamide blocks, but also a small proportion of the various reactants randomly distributed along the polymer chain. As in the first stage of the two-stage process described above, the reactor is closed and heated with stirring. The pressure produced is between 5 and 30 bar. When the pressure stops changing, the reactor is placed under reduced pressure while continuing to vigorously stir the molten reactants. The reaction is monitored as before in the case of the two-step process.

The correct ratio of polyamide to polyether blocks can be found in a single poly(ether block amide) or a blend of two or more different compositions of poly(ether block amide)s can be used with the correct average composition. In one aspect, it can be helpful to have a block copolymer that has a high proportion of polyamide groups to blend with a block copolymer having a higher proportion of polyether blocks to produce a blend having an average proportion of polyether blocks of about 20 to 40 percent by weight of the total blend of poly(amide-block-ether) copolymers and preferably about 30 to 35% by weight. In another aspect, the copolymer comprises a blend of two different poly(ether block amides) comprising at least one block copolymer having a proportion of polyether blocks that is less than about 35% by weight and a second poly(ether block block amide) having at least about 45% by weight polyether blocks.

In various aspects, the thermoplastic polymer is a polyamide or a poly(ether block amide) having a melting temperature (T _m ) of from about 90°C to about 120°C when used in accordance with AS T _m D3418-97 as further herein described below. In another aspect, the thermoplastic polymer is a polyamide or a poly(ether block amide) having a melting temperature (T _m ) of from about 93°C to about 99°C when used in accordance with AS T _m D3418-97 as herein described below. In yet another aspect, the thermoplastic polymer is a polyamide or a poly(ether block amide) having a melting temperature ( _Tm ) of from about 112°C to about 118°C when used in accordance with AS _Tm D3418-97, such as described hereinbelow. In some aspects, the thermoplastic polymer is a polyamide or a poly(ether block amide) having a melting temperature of about 90°C, about 91°C, about 92°C, about 93°C, about 94°C, about 95°C , about 96°C, about 97°C, about 98°C, about 99°C, about 100°C, about 101°C, about 102°C, about 103°C, about 104°C, about 105°C, about 106°C, about 107°C, about 108°C, about 109°C, about 110°C, about 111°C, about 112°C, about 113°C, about 114°C, about 115°C, about 116°C, about 117°C, about 118°C, about 119°C, about 120°C, any range of melting temperature (T _m ) values included in any of the above values, or any one Combination of the above melting temperature (T _m ) values when determined in accordance with AS T _m D3418-97 as described herein below.

In various aspects, the thermoplastic polymer is a polyamide or a poly(ether block amide) having a glass transition temperature (T _g ) of from about -20°C to about 30°C when determined according to ASTM D3418-97, as described below. In another aspect, the thermoplastic polymer is a polyamide or a poly(ether block amide) having a glass transition temperature (T _g ) of from about -13°C to about -7°C when determined according to ASTM D3418-97 as described below . In another aspect, the thermoplastic polymer is a polyamide or a poly(ether block amide) having a glass transition temperature (T _g ) of from about 17°C to about 23°C when determined according to ASTM D3418-97, as described below. In some aspects, the thermoplastic polymer is a polyamide or a poly(ether block amide) having a glass transition temperature (T _g ) of about -20°C, about -19°C, about -18°C, about -17°C, about -16 °C, about -15°C, about -14°C, about -13°C, about -12°C, about -10°C, about -9°C, about -8°C, about -7°C , about -6°C, about -5°C, about -4°C, about -3°C, about -3°C, about -3°C, about -3°C, about -8°C, about -7°C, about -6°C, about -5°C, about -4°C, about -3°C, about -3°C, about -3°C, about -3°C, about -2 °C, about -1°C, about 0°C, about 1°C, about 2°C, about 3°C, about 4°C, about 5°C, about 6°C, about 7°C, about 8°C, about 9°C, about 10°C, about 11°C, about 12°C, about 13°C, about 14°C, about 15°C, about 16°C, about 17°C, about 18°C, about 19°C, about 20°C, any glass transition temperature values encompassed by any of the above values, or a combination of the above glass transition temperature values when determined according to ASTM D3418-97 as described below.

In various aspects, the thermoplastic polymer is a polyamide or a poly(ether block amide) having a melt flow index of from about 10 ^cc /10 min to about 30 ^cc /10 min when measured at 160° according to ASTM D1238-13, as described below C is tested at a weight of 2.16 kg. In another aspect, the thermoplastic polymer is a polyamide or a poly(ether block amide) having a melt flow index of from about 22 ^cc /10 min to about 28 ^cc /10 min when tested at 160 according to ASTM D1238-13, as described below °C is tested with a weight of 2.16 kg. In some aspects, the thermoplastic polymer is a polyamide or a poly(ether block amide) having a melt flow index of about 10 ^cc /10 min, about 11 ^cc /10 min, about ¹² cc/10 min, about ¹³ cc/10 min , about 14 cc ^/ 10 min, about 15 ^cc /10 min, about 16 ^cc /10 min, about 17 ^cc /10 min, about 18 ^cc /10 min, about ¹⁹ cc/10 min, about 20 ^cc /10 min, about 21 ^cc /10 min, about 23 ^cc /10 min, about 24 ^cc /10 min, about 25 cc/10 min, about 26 ^cc /10 min, about ^{27 cc} /10 min /10 min, about 28 cc ^/ 10 min, about 29 ^cc /10 min, about 30 ^cc /10 min, any range of melt flow index values encompassed by any of the foregoing values, or any combination of the foregoing melt flow index values when determined according to ASTM D1238-13 as described below at 160°C with a 2.16 kg weight.

In various aspects, the thermoplastic polymer is a polyamide or a poly(ether block amide) having a Ross Cold Bend Test result of from about 120,000 to about 180,000 when formed on a thermoformed plaque of the polyamide or poly(ether block amide) according to the Ross procedure described below. cold bend test is tested. In another aspect, the thermoplastic polymer is a polyamide or a poly(ether block amide) having a Ross cold bend test result of about 140,000 to about 160,000 when applied to a thermoformed plaque of the polyamide or poly(ether block amide) according to the Ross described below -Cold bend test being tested. In another aspect, the thermoplastic polymer is a polyamide or a poly(ether block amide) having a Ross Cold Bend Test result of about 130,000 to about 170,000 when applied to a thermoformed plaque of the polyamide or poly(ether block amide) according to the Ross described below -Cold bend test being tested. In some aspects, the thermoplastic polymer is a polyamide or a poly(ether block amide) having a Ross Cold Bend Test result of about 120,000, about 125,000, about 130,000, about 135,000, about 140,000, about 145,000, about 160,000, about 165,000, about 170,000 about 175,000 , approximately 180,000, any range of cold Ross Flex test values encompassed by any one of the above values or any combination of the above Ross cold flex test test values when applied to a thermoformed plaque of the polyamide or poly(ether block amide) according to the Ross procedure described below Cold bend test to be tested.

In various aspects, the thermoplastic polymer is a polyamide or a poly(ether block amide) having a modulus of from about 5 MPa to about 100 MPa when applied to a thermoformed plaque according to ASTM-D412-98 Standard Test Methods for Vulcanized Rubbers and Thermoplastic Rubbers and Thermoplastic Elastomer Stress is determined with modifications described below. In another aspect, the thermoplastic polymer is a polyamide or a poly(ether block amide) having a modulus of from about 20 MPa to about 80 MPa when applied to a thermoformed plaque according to ASTM-D412-98 Standard Test Methods for Vulcanized Rubbers and Thermoplastic Rubbers and Thermoplastic Elastomer Stress is determined with modifications described below. In some aspects, the thermoplastic polymer is a polyamide or a poly(ether block amide) having a modulus of about 5 MPa, about 10 MPa, about 15 MPa, about 20 MPa, about 25 MPa, about 30 MPa, about 35 MPa, about 40 MPa , about 65 MPa, about 70 MPa, about 75 MPa, about 80 MPa, about 85 MPa, about 90 MPa, about 95 MPa, about 100 MPa, any range of modulus values encompassed by any of the above values, or a combination of the modulus values above when determined on a thermoformed plaque of the polyamide or the poly(ether block amide) according to ASTM-D412-98 Standard Test Method for Vulcanized Rubbers and Thermoplastic Rubbers and Thermoplastic Elastomer Stress with modifications described below.

In various aspects, the thermoplastic polymer is a polyamide or a poly(ether block amide) having a melting temperature (T _m ) of about 115°C when determined according to ASTM D3418-97 as described below; a glass transition temperature (T _g ) of about -10°C when determined according to ASTM D3418-97 as described below; a melt flow index of about 25 ^cc /10 min when tested according to ASTM D1238-13, as described below, at 160°C with a 2.16 kg weight; a Ross Cold Bend Test result of about 150,000 when tested on a thermoformed plaque according to the Ross Cold Bend Test described below; and a modulus of from about 25 MPa to about 70 MPa when determined on a thermoformed plaque according to ASTM-D412-98 Standard Test Methods for Vulcanized Rubbers and Thermoplastic Rubbers and Thermoplastic Elastomer Stress with modifications described below.

In various aspects, the thermoplastic polymer is a polyamide or a poly(ether block amide) having a melting temperature (T _m ) of about 96°C when determined according to ASTM D3418-97, as described below; a glass transition temperature (T _g ) of about 20°C when determined according to ASTM D3418-97 as described below; a Ross Cold Bend Test result of about 150,000 when tested on a thermoformed plaque according to the Ross Cold Bend Test described below; and a modulus of less than or equal to about 10 MPa when determined on a thermoformed plaque in accordance with ASTM D412-98 Standard Test Methods for Vulcanized Rubbers and Thermoplastic Rubbers and Thermoplastic Elastomer Stress with modifications described below.

In various aspects, the thermoplastic polymer is a polyamide or a poly(ether block amide), a blend of a first polyamide or a poly(ether block amide) having a melting temperature (T _m ) of about 115°C when prepared according to ASTM D3418-97, as follows described, determined; a glass transition temperature (T _g ) of about -10°C when measured according to ASTM D3418-97, as follows described, determined; a melt flow index of about 25 ^cc /10 min when tested according to ASTM D1238-13, as described below, at 160°C with a 2.16 kg weight; a Ross Cold Bend Test result of about 150,000 when tested on a thermoformed plaque according to the Ross Cold Bend Test described below and a modulus of from about 25 MPa to about 70 MPa when tested on a thermoformed plaque according to ASTM-D412-98 Standard Test Method for vulcanized rubbers and thermoplastic rubbers and thermoplastic elastomer stress is determined with modifications described below; and a second polyamide or a poly(ether block amide) having a melting temperature (T _m ) of about 96°C when determined according to ASTM D3418-97 as described below; a glass transition temperature (T _g ) of about 20°C when determined according to ASTM D3418-97 as described below; a Ross Bend Test result of about 150,000 when tested on a thermoformed plaque according to the Ross Bend Test described below; and a modulus of less than or equal to about 10 MPa when determined on a thermoformed plaque in accordance with ASTM D412-98 Standard Test Methods for Vulcanized Rubbers and Thermoplastic Rubbers and Thermoplastic Elastomer Stress with modifications described below.

Examples of commercially available copolymers include the copolymers available under the trade names ^VESTAMID® (Evonik Industries). ^PLATAMID® (Arkema), e.g. B., product code H2694; ^PEBAX® (Arkema), e.g. B. Product code "PEBAX MH1657" and "PEBAX MV1074"; ^PEBAX® RNEW (Arkema); GRILAMID ^® (EMS-Chemie AG) or similar materials that are manufactured by various other suppliers.

In some examples the thermoplastic polyamide is physically bonded by e.g. B. non-polar or polar interactions between the polyamide groups of the polymers are intertwined. In examples where the thermoplastic polyamide is a thermoplastic copolyamide, the thermoplastic copolyamide can be physically crosslinked through interactions between the polyamide groups, optionally through interactions between the copolymer groups. When the thermoplastic copolyamide is physically crosslinked, the polyamide segments can form what is called the "hard segment" of the polymer and copolymer segments can form what is called the "soft segment" of the polymer. For example, when the thermoplastic copolyamide is a thermoplastic poly(ether block amide), the polyamide segments form the hard segment portion of the polymer and polyether segments can form the soft segment portion of the polymer. Thus, in some examples, the thermoplastic polymer may include a physically crosslinked polymeric network having one or more amide-linked polymer chains.

In some aspects, the polyamide segment of the thermoplastic copolyamide comprises polyamide-11 or polyamide-12 and the polyether segment is a segment selected from the group consisting of polyethylene oxide, polypropylene oxide, and polytetramethylene oxide segments, and combinations thereof.

Optionally, the thermoplastic polyamide can be partially covalently crosslinked as described herein. In such cases, it is believed that the degree of crosslinking present in the thermoplastic polyamide is such that when thermally processed in the form of a yarn or fiber into the footwear of the present disclosure, the partially covalently crosslinked thermoplastic polyamide is sufficiently thermoplastic such that the partially covalently crosslinked thermoplastic polyamide is softened or melted during processing.

thermoplastic polyesters

In aspects, the thermoplastic polymers can be made of a thermoplastic polyester. The thermoplastic polyester can be formed by reacting one or more carboxylic acids or its ester-forming derivatives with one or more divalent or multivalent aliphatic, alicyclic, aromatic or araliphatic alcohols or a bisphenol. The thermoplastic polyester can be a polyester homopolymer having repeating polyester segments of the same chemical structure. Alternatively, the polyester can include a variety of polyester segments having different polyester chemical structures (e.g., polyglycolic acid segments, polylactic acid segments, polycaprolactone segments, polyhydroxyalkanoate segments, polyhydroxybutyrate segments, etc.). The polyester segments with different chemical structure can be arranged randomly or as repeating blocks.

Exemplary carboxylic acids that can be used to make a thermoplastic polyester include, but are not limited to, adipic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, terephthalic acid, isophthalic acid, alkyl-substituted or halogenated terephthalic acid, alkyl-substituted or halogenated isophthalic acid, nitroterephthalic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylthieutherdicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 4,4'-diphenylalkylenedicarboxylic acid, naphthalene-2,6-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid and Cyclohexane-1,3-dicarboxylic acid. Exemplary diols or phenols suitable for preparing the thermoplastic polyester include, but are not limited to, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1, 8-octanediol, 1,10-decanediol, 1,2-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2,4-trimethylhexanediol, p-xylenediol, 1,4-cyclohexanediol, 1,4- cyclohexane dimethanol and bis-A phenol.

In some aspects, the thermoplastic polyester is a polybutylene terephthalate (PBT), a polytrimethylene terephthalate, a polyhexamethylene terephthalate, a poly-1,4-dimethylcyclohexane terephthalate, a polyethylene terephthalate (PET), a polyethylene isophthalate (PEI), a polyarylate (PAR), a polybutylene naphthalate (PBN ), a liquid crystal polyester, or a mixture or blend of two or more of the foregoing.

The thermoplastic polyester can be a co-polyester (i.e. a co-polymer having polyester segments and non-polyester segments). The co-polyester can be an aliphatic co-polyester (i.e., a co-polyester in which both the polyester segments and the non-polyester segments are aliphatic). Alternatively, the co-polyester can contain aromatic segments. The polyester segments of the co-polyester may comprise or consist of polyglycolic acid segments, polylactic acid segments, polycaprolactone segments, polyhydroxyalkanoate segments, polyhydroxybutyrate segments, or any combination thereof. The polyester segments of the co-polyester can be arranged randomly or as repeating blocks.

For example, the thermoplastic polyester can be a block copolyester with repeating blocks of polymeric units of the same chemical structure (segments) that are relatively harder (hard segments) and repeating blocks of polymeric segments that are relatively softer (soft segments). In block copolyesters, including block copolyesters with repeating hard segments and soft segments, physical crosslinks can be present within the blocks or between the blocks, or both within and between the blocks. In a particular example, the thermoplastic material may consist essentially of an elastomeric thermoplastic co-polyester containing hard segment repeating blocks and soft segment repeating blocks.

The non-polyester segments of the co-polyester may include or consist of polyether segments, polyamide segments, or both polyether segments and polyamide segments. The co-polyester can be a block co-polyester or a random co-polyester. The thermoplastic co-polyester can be formed from the polycondensation of a polyester oligomer or prepolymer with a second oligomer-prepolymer to form a block copolyester. Optionally, the second prepolymer can be a hydrophilic prepolymer. For example, the co-polyester can be formed from the polycondensation of terephthalic acid or naphthalenedicarboxylic acid with ethylene glycol, 1,4-butanediol, or 1-3 propanediol. Examples of co-polyesters are polyethelene adipate, polybutylene succinate, poly(3-hydroxybutyrate-co-3-hydroxyvalerate), polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, and combinations thereof. In a specific example, the copolyamide may comprise or consist of polyethylene terephthalate.

In some aspects, the thermoplastic polyester is a block copolymer containing segments of one or more polybutylene terephthalate (PBT), a polytrimethylene terephthalate, a polyhexamethylene terephthalate, a poly-1,4-dimethylcyclohexane terephthalate, a polyethylene terephthalate (PET), a polyethylene isophthalate (PEI), a polyarylate ( PAR), a polybutylene naphthalate (PBN) and a liquid crystal polyester. A suitable thermoplastic polyester that is a block copolymer may be, for example, a PET/PEI copolymer, a polybutylene terephthalate/tetraethylene glycol copolymer, a polyoxyalkylenediimide diacid/polybutylene terephthalate copolymer, or a mixture or blend of any of the foregoing.

In some aspects, the thermoplastic polyester is a biodegradable resin, e.g. B. a copolymerized polyester in which poly(A-hydroxy acid) such as polyglycolic acid or polylactic acid is contained as main repeating units.

The disclosed thermoplastic polyesters can be prepared using a variety of polycondensation methods known to those skilled in the art, such as e.g. B. a solution polymerization or a melt polymerization process.

thermoplastic polyolefins

In some aspects, the thermoplastic polymers may consist essentially of or comprise a thermoplastic polyolefin. Examples of thermoplastic polyolefins can include, but are not limited to, polyethylene, polypropylene, and olefin thermoplastic elastomers (e.g., metallocene-catalyzed block copolymers of ethylene and olefins having from 4 to about 8 carbon atoms). In another aspect, the thermoplastic polyolefin is a polymer selected from a polyethylene, an ethylene-olefin copolymer, an ethylene-propylene rubber (EPDM), a polybutene, a polyisobutylene, a poly-4-methyl-1-pentene, a polyisoprene, a polybutadiene, an ethylene methacrylic acid copolymer, and an olefin elastomer such as a dynamically crosslinked polymer of polypropylene (PP) and an ethylene propylene rubber (EPDM), and mixtures or blends of the foregoing. Other exemplary thermoplastic polyolefins useful in the disclosed compositions, yarns and fibers are polymers of cycloolefins such as cyclopentene or norbornene.

It is understood that polyethylene, which can be optionally crosslinked, is a variety of polyethylenes including, but not limited to, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE), Medium Density Polyethylene (MDPE), High Density Polyethylene (HDPE), High Density Polyethylene of High Molecular Weight (HDPE-HMW), High Density Polyethylene of Ultra High Molecular -Weight (HDPE-UHMW). A polyethylene can also be a polyethylene copolymer derived from monoolefins and diolefins copolymerized with vinyl, acrylic acid, methacrylic acid, ethyl acrylate, vinyl alcohol and/or vinyl acetate. Polyolefin copolymers containing vinyl acetate derived units may be a high vinyl acetate content copolymer, e.g. B. greater than about 50% by weight of vinyl acetate-derived composition.

In some aspects, the thermoplastic polyolefin as disclosed herein can be formed by free radical, cationic, and/or anionic polymerization by methods known to those skilled in the art (e.g., with a peroxide initiator, heat, and/or light). In another aspect, the disclosed thermoplastic polyolefin can be prepared by high pressure, elevated temperature free radical polymerization. Alternatively, the thermoplastic polyolefin may be prepared by catalytic polymerisation with a catalyst normally containing one or more of Group IVb, Vb, VIb or VIII metals. The catalyst usually has one or more ligands, typically oxides, halides, alcoholates, esters, ethers, ethers, alkyls, alkenyls and/or aryls, which are either p- or s-coordinated to Group IVb, Vb, Vlb or VIII Metal can be complexed. In various aspects, the metal complexes can be in free form or affixed to substrates, typically activated magnesium chloride, titanium (III) chloride, alumina or silica. It is understood that the metal catalysts can be soluble or insoluble in the polymerization medium. The catalysts themselves can be used in the polymerisation or further activators can be used, typically a Group Ia, Ila and/or IIIa metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes. The activators can be conveniently modified with additional ester, ether, amine, or silyl ether groups.

Suitable thermoplastic polyolefins can be made by polymerizing mono-olefins and di-olefins as described herein. Exemplary monomers that can be used to prepare disclosed thermoplastic polyolefin include, but are not limited to, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 2-methyl-1-propene, 3 -Methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene and mixtures thereof.

Suitable ethylene-olefin copolymers can be obtained by copolymerizing ethylene with an olefin such as propylene, butene-1, hexene-1, octene-1,4-methyl-1-pentene or the like having from 3 to 12 carbon numbers.

Appropriate dynamically crosslinked polymers can be obtained by crosslinking a rubber component as a soft segment and at the same time a hard segment such as PP and a soft segment such as EPDM can be physically dispersed with a kneading machine such as a Banbbury mixer and a biaxial extruder.

In some aspects, the thermoplastic polyolefin can be a blend of thermoplastic polyolefins, such as. B. a blend of two or more polyolefins disclosed above. A suitable mixture of thermoplastic polyolefins can be, for example, a mixture of polypropylene with polyisobutylene, polypropylene with polyethylene (e.g. PP/HDPE, PP/LDPE) or mixtures of different types of polyethylene (e.g. LDPE/HDPE).

In some aspects, the thermoplastic polyolefin can be a copolymer of suitable monoolefin monomers or a copolymer of a suitable monoolefin monomer and a vinyl monomer. Exemplary thermoplastic polyolefin copolymers include, but are not limited to, ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and blends thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene Copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/alkyl acrylate - Copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers, copolymers with carbon monoxide or ethylene/acrylic acid copolymers and their salts (ionomers) and terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene norbornene; and mixtures of such copolymers with each other and with polymers mentioned in 1) above, e.g. B. Polypropylene/ethylene propylene copolymers, LDPE/ethylene vinyl acetate copolymers (EVA), LDPE/ethylene acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/carbon monoxide copolymers and blends thereof with other polymers , e.g. B. Polyamides.

In some aspects, the thermoplastic polyolefin can be a polypropylene homopolymer, a polypropylene copolymer, a polypropylene random copolymer, a polypropylene block copolymer, a polyethylene homopolymer, a polyethylene random copolymer, a low density polyethylene copolymer (LDPE), a linear Low Density Polyethylene (LLDPE), a Medium Density Polyethylene, a High Density Polyethylene (HDPE), or blends or blends.

In some aspects, the polyolefin is a polypropylene. The term "polypropylene" as used herein is intended to include any polymeric composition comprising propylene monomers, either alone or in admixture, or copolymers with other randomly selected and oriented polyolefins, dienes, or other monomers (such as ethylene, butylene, and the like). Such a term also encompasses any different configuration and arrangement of the constituent monomers (such as atactic, syndiotactic, isotactic, and the like). Thus, as applied to fibers, the term is intended to encompass actual long strands, ribbons, filaments and the like of drawn polymer. The polypropylene can be of any standard melt flow (by inspection), however, standard fiber polypropylene resins have melt flow index ranges between about 1 and 1000.

In some aspects, the polyolefin is a polyethylene. The term "polyethylene" as used herein is intended to include any polymeric composition comprising ethylene monomers, either alone or in admixture, or copolymers with other randomly selected and oriented polyolefins, dienes, or other monomers (such as propylene, butylene, and the like). Such a term also encompasses any different configuration and arrangement of the constituent monomers (such as atactic, syndiotactic, isotactic, and the like). Thus, as applied to fibers, the term is intended to encompass actual long strands, ribbons, filaments and the like of drawn polymer. The polyethylene can be of any standard melt flow (by inspection), however standard fiber polyethylene resins have melt flow index ranges between about 1 and 1000.

Methods of making resin compositions

In various aspects, this disclosure also provides a method of making a resin composition, the method including mixing a polypropylene copolymer and an effective amount of a polymer resin modifier, wherein the effective amount of the polymer resin modifier is effective for the resin composition to pass a flex test according to the Ross cold flex test the plaque sampling procedure.

There is provided a method of making a resin composition, the method comprising mixing a polypropylene copolymer and an effective amount of a polymeric resin modifier, wherein the effective amount of the polymeric resin modifier is effective for the resin composition to undergo a flex test according to the Ross Cold Bend Test with the Plaque Sampling Method can exist without significant change in abrasion loss when measured according to ASTM D 5963-97a using the sampling method.

The resin compositions herein can be prepared by blending an effective amount of a polymeric resin modifier and a polyolefin copolymer into a blended resin composition, the effective amount being as described above. The methods of blending polymers may include sheet blending in a press, blending in a blender (e.g., blenders available under the tradename "HAAKE" from Thermo Fisher Scientific, Waltham, MA), solution blending, melt blending and extruder mix. In some aspects, the polymer resin modifier and the polyolefin copolymer are so miscible that they can be easily mixed by the screw mixer in the injection run during injection molding, e.g. B. without a separate mixing step.

The resin compositions herein can be prepared by admixing an effective amount of an isotactic polyolefin copolymer resin modifier, the effective amount being an effective amount for the resin composition to pass a flex test according to the Ross Cold Bend Test using the Plaque Sampling Method, wherein a second resin composition, which is identical to the resin composition except without the isotactic polyolefin copolymer resin modifier fails the flex test according to the Ross cold flex test with the plaque sampling method. The effective amount can be effective to maintain an attrition loss of the resin composition within about 20% of an attrition loss of the second resin composition according to ASTM D 5963-97a in the material testing procedure. The effective amount can be the effective amount of the isotactic polyolefin copolymer resin modifier that reduces a percent crystallization of the resin composition by at least 4 percentage points compared to a percent crystallization of the second resin composition when measured by the Differential Scanning Calorimeter (DSC) Test is measured with the material sampling method.

The methods may further include extruding the blended resin composition into an extruded resin composition. Processes for extruding the blended resin may involve the manufacture of long, relatively constant cross-section products (rod, sheet, tube, foil, wire insulation coating). The methods of extruding the blended resin may include feeding a softened blended resin composition through a die having an orifice. The mixed resin can be conveyed forward by a feed screw and pushed through the nozzle. Heating elements placed over the barrel can soften and melt the mixed resin. The temperature of the material can be controlled by thermocouples. The product emerging from the die can be cooled by forced air or in a water bath to form the extruded resin composition. Alternatively, the product emerging from the die can be granulated with little cooling as described below.

The method may further include granulating the extruded resin composition into a granulated resin composition. Methods of granulation can include melt granulation (hot cut), in which the melt coming out of a die is almost instantaneously cut into pellets, which are liquid or gas conveyed and cooled. Granulation methods may include strand pelletization (cold cut), in which the melt coming from the die is converted into strands (the extruded resin composition), which after cooling and solidification are cut into pellets.

The method may also include injection molding the pelletized resin composition into an article. Injection molding may involve the use of a non-rotating, cold piston to force the pelletized resin through a heated barrel, with the resin composition being heated by heat conducted from the walls of the barrel to the resin composition. Injection molding may involve the use of a rotating screw coaxial with a heated barrel to convey the pellet resin composition to a first end of the screw and heat the resin composition by conduction of heat from the heated barrel to the resin composition. As the resin composition is fed to the first end by the screw mechanism, the screw is translated to the second end to create a reservoir space at the first end. When sufficient melt resin composition is collected in the reservoir space, the screw mechanism can be shifted to the first end to inject the material into a selected mold.

Methods of crafting components and items

The disclosure includes various methods of making components and articles described herein. The methods can include injection molding a resin composition as described herein. The disclosure provides methods of making a component for an article of footwear or athletic equipment by injection molding a resin composition described herein.

The methods can further include providing a component containing a resin composition and providing a second element and attaching the component to the second element. The second element may contain a textile or multilayer film. The second element can e.g. B. contain an upper part. The second element may contain one or both polyolefin fibers and polyolefin yarns.

In some aspects, polyolefin is present on a side or outer layer of the second member and the method includes attaching the polyolefins together. The second element may include a yarn, textile, foil, or other element. Attaching the component to the second member may include injecting the resin composition directly into the second member. Attaching the component to the second element may include forming a mechanical bond between the resin composition and the second element. Attaching the component to the second member may include (i) raising the resin composition to a first temperature above a melting or softening point of the resin composition, (ii) contacting the resin composition and the second member during the first temperature of the resin composition, and (iii) keeping the resin composition and the second member in contact with each other while raising the temperature of the resin composition to a second temperature below the melting temperature or softening point of the resin composition, forming a mechanical bond between the resin composition and the second member.

The second element may be a thermoplastic polymeric material, and attaching the component to the second element may include (i) raising the temperature of the thermoplastic polymeric material to a first temperature above a melting or softening point of the thermoplastic polymeric material, (ii) attaching the resin composition and the second element while the thermoplastic polymeric material is at the first temperature, and (iii) maintaining the resin composition and the second element in contact with each other while raising the temperature of the thermoplastic polymeric material to a second temperature below the melting or softening point of the thermoplastic polymeric material and form a mechanical bond between the resin composition and the second element.

The second element may contain a thermoplastic polymeric material, and attaching the component to the second element may (i) raising a temperature of both the resin composition and the thermoplastic polymeric material to a first temperature above a melting or softening point of the resin composition and a melt - or softening point of the thermoplastic polymeric material, (ii) keeping the resin composition and the second element in contact while both the resin composition and the thermoplastic polymeric material are at the first temperature and (iii) keeping the resin composition and the second element in contact with each other and at the same time reducing the temperature of both the resin composition and the thermoplastic polymeric material to a second temperature below the melting or softening point of the resin composition and the melting or softening point of the thermoplastic polymeric material, thereby fusing at least a portion of the resinous material and the thermoplastic polymeric material together, thereby forming a mechanical bond is formed between the resin composition and the second member.

In some aspects, the article is an article of footwear and the method includes injection molding a plate as described herein. The method may include providing the panel, providing a top, and attaching the panel and top.

Property analysis and characterization methods

Ross cold bend test

The Ross cold bend test is determined according to the following test method. The purpose of this test is to evaluate the resistance to cracking of a specimen when repeatedly flexed to 60 degrees in a cold environment. A thermoformed plaque of the material to be tested is sized to fit the Flextester machine. Each material is tested as five separate samples. The Flextester machine is capable of bending samples to 60 degrees at a rate of 100 +/- 5 cycles per minute. The mandrel diameter of the machine is 10 millimeters. Suitable machines for this test are the Emerson AR-6, the Satra ST _m 141F, the Gotech GT-7006 and the Shin II Scientific SI-LTCO (DaeSung Scientific). The samples are fed into the machine according to the specific parameters of the flex machine used. The machine is placed in a freezer at -6 °C for the test. The motor is turned on to begin counting the flex cycles until the sample breaks. Cracking of the specimen means that the surface of the material is physically divided. Visible folds of lines that don't actually penetrate the surface are not tears. The sample is measured to a point where it has cracked but not yet broken in two.

Abrasion Loss Test ASTM D 5963-97a

The abrasion loss is tested on cylindrical specimens with a diameter of 16 x 0.2 mm and a minimum thickness of 6 mm made from sheet metal using an ASTM standard drill. Attrition loss is measured using Method B of ASTM D 5963-97a on a Gotech GT-7012-D abrasion testing machine. The tests are carried out at 22 °C with an abrasion distance of 40 meters. The standard #1 rubber used in the tests has a density of 1.336 grams per cubic centimeter (g/cm ³ ). The smaller the abrasion volume, the better the abrasion resistance.

mud pull test method

A two inch diameter sample of material is cut on a standard mechanical testing machine (e.g. Instron Tensile Tester) and mounted on the top plate of a set of parallel flat aluminum test plates. A sample of mud approximately 7 millimeters high and 1 inch in diameter is loaded onto the bottom plate of the mechanical tester. The soil used to prepare the mud is commercially available under the trade name "TIMBERLINE TOP SOIL", model 50051562, from Timberline (a subsidiary of Old Castle, Inc., Atlanta, Ga.) and was constructed using a square mesh with a Sieved to a pore dimension of 1.5 millimeters on each side. The sludge was previously dried and then diluted to 22% by weight of water. The force converters are normalized to zero force. The plates are then compressed in the direction of compression to a load of 445 Newtons. The load is then immediately removed and a small force hysteresis is measured at the sludge detachment point, which is greater than the zero tarred value in the pull direction. The maximum force measured is the pull-off force for mud adhesion to the material substrate. The compression/detachment cycle is repeated at least 10 times until a stable value is reached.

Differential Scanning Calorimeter (DSC) test

To determine the percentage crystallinity of a resin composition including a copolymer and a polymer resin modifier, samples of the copolymer, the resin composition and a homopolymer of the main component of the copolymer (e.g. polypropylene-homopolymer-polypropylene) are measured by differential scanning calorimetry (DSC) over the Temperature range analyzed from -80 °C to 250 °C. A heating rate of 10°C per minute is used. The melting endotherm is measured for each sample during heating. Universal Analysis Software (TA Instruments, New Castle, DE, USA) is used to calculate percent crystallinity (% crystallinity) based on the melting endotherm for the homopolymer (eg, 207 joules per gram for 100% crystalline polypropylene material). In particular, percent crystallinity (% crystallinity) is calculated by dividing the melting endotherm measured for the copolymer or resin composition by the 100% crystalline homopolymer melting endotherm.

Method for determining the creep ratio temperature T _cr .

The creep ratio temperature T _cr is determined according to the exemplary techniques described in U.S. Patent No. 5,866,058 are described. The creep ratio temperature T _cr is the temperature at which the stress relaxation modulus of the tested material is 10% relative to the stress relaxation modulus of the tested material at the solidification temperature of the material, the stress relaxation modulus being measured according to ASTM E328-02. The solidification temperature is defined as the temperature at which the stress relaxation modulus changes little to not at all or can creep little to no approximately 300 seconds after application of a stress to a test material, as determined by plotting the stress relaxation modulus (in Pa) as a function of temperature ( in °C) can be observed.

Procedure for determining the Vicat softening point Tvs

The Vicat Softening Temperature T _vs is according to the test method described in ASTM D1525-09 (Standard Test Method for Vicat Softening Temperature of Plastics), preferably using stress A and determine rate A. Briefly, the Vicat softening point is the temperature at which a flattened needle penetrates the specimen to a depth of 1mm under a specific load. Temperature reflects the softening point expected when a material is used in an elevated temperature application. It is taken as the temperature at which the specimen is penetrated to a depth of 1 mm by a flattened needle of circular or square cross-section of 1 mm ² . A load of 10N is used for the Vicat A test, whereas the load for the Vicat B test is 50N. The test involves placing a test specimen in the test device so that the penetrating needle rests on its surface at least 1mm from the edge. A load is applied to the specimen according to the requirements of the Vicat A or Vicat B test. The specimen is then lowered into an oil bath at 23°C. The bath is then increased at a rate of 50°C or 120°C per hour until the needle penetrates to 1mm. The test specimen shall be between 3 and 6.5mm thick and at least 10mm wide and 10mm long. No more than three layers can be stacked to achieve the minimum thickness.

Procedure for determining heat distortion temperature T _hd .

The deflection temperature T _hd is according to the test method described in ASTM D648-16 (Standard Test Method for Deflection Temperature of Plastics Under Flexural Load in the Edgewise Position), to be determined using an applied stress of 0.455 MPa. Briefly stated, heat deflection temperature is the temperature at which a polymer or plastic sample will deform under a specified load. This property of a given plastic material is applied in many aspects of product design, engineering and manufacture of products using thermoplastic components. In the test procedure, the bars are placed under the deflection gauge and a load (0.455 MPa) is applied to each specimen. The specimens are then lowered into a silicone oil bath where the temperature is increased at 2°C per minute until they deflect 0.25 mm per ASTM D648-16. ASTM uses a standard 5" x 1/2" x 1/4" bar. An ISO portrait test uses a 120mm x 10mm x 4mm rod. An ISO flat edge test uses an 80mm x 10mm x 4mm rod.

Methods for determining the melting temperature, T _m , and the glass transition temperature, T _g .

The melting temperature, T _{m ,} and the glass transition temperature, T _g , are determined using a commercially available differential scanning calorimeter ("DSC") according to ASTM D3418-97. Briefly, a 10-15 gram sample is placed in an aluminum DSC crucible and then the lead is sealed with the crimping press. The DSC is configured to run from -100°C to 225°C at a heating rate of 20°C/minute, hold at 225°C for 2 minutes and then cool to 25°C at a rate of -10°C /minute to scan. The DSC curve generated from this scan is then analyzed using standard techniques to determine the glass transition temperature, _Tg , and the melting temperature, _Tm .

Method of determining melt index.

Melt Index is determined according to the test method described in ASTM D1238-13 (Standard Test Method for Melt Flow Rates of Thermoplastics by Extrusion Plastometer), using Procedure A described therein . Briefly, melt index measures the rate of extrusion of thermoplastics through an orifice at a specified temperature and load. In the test procedure, approximately 7 grams of material is placed in the barrel of the melt flow apparatus, which is then heated to a temperature specified for the material. A weight specified for the material is applied to a plunger and the molten material is forced through the nozzle. A timed extrudate is collected and weighed. Melt flow rate values are calculated in g/10 min.

Method for determining the modulus (plaque).

The modulus for a thermoformed plaque of material is determined according to the test method described in ASTM D412-98 (Standard Test Methods for Vulcanized Rubber and Thermoplastic Rubbers and Thermoplastic Elastomers-Tension). , with the following modifications. The sample dimension is die C of ASTM D412-98 and the sample thickness used is 2.0 millimeters +/- 0.5 millimeters. The type of gripper used is a pneumatic gripper with a serrated metal gripping surface. The gripping distance used is 75 millimeters. The load rate used is 500 mm/minute. The modulus (initial) is calculated by taking the slope of the stress (MPa) compared to the strain in the initial linear region.

Procedure for determining the modulus (yarn).

The modulus for a yarn is determined according to the test method specified in EN ISO 2062 ((Textiles-Yarns from Packages) - Determination of Single-End Breaking Force and Elongation at Break Using Constant Rate of Extension (CRE) Tester, dt. "(Textilien - Yarns from packages) - Determination of breaking force for individual ends and elongation at break using a constant rate elongation tester (CRE tester)") with the following modifications. The sample length used is 600 mm. The equipment used is an Instron and Gotech device. The gripping distance used is 250 millimeters. The preload is set at 5 grams and the load rate used is 250 millimeters/minute. The first meter of yarn is discarded to avoid using damaged yarn. The (initial) modulus is calculated by taking the slope of the stress (MPa) compared to the strain in the initial linear region.

Method for determining tensile strength and tensile elongation.

Tensile strength and elongation at break of yarn can be determined according to the test method specified in EN ISO 2062, Determination of single end breaking force and elongation at break using constant rate of extension tester Using a Constant Rate Elongation Tester"), with the preload set at 5 grams.

Procedure for determining shrinkage.

The free shrinkage of fibers and/or yarns can be determined by the following procedure. A sample fiber or yarn is cut to a length of about 30 millimeters with minimal tension at about room temperature (e.g. 20°C). The cut sample is placed in an oven at 50°C or 70°C for 90 seconds. The sample is removed from the oven and measured. Percent shrinkage is calculated using the measurements of the sample before and after the oven by dividing the measurement after the oven by the measurement before the oven and multiplying by 100.

Procedure for determining the enthalpy of fusion.

The enthalpy of fusion is determined by the following procedure. A fiber or yarn sample of 5-10 mg is weighed to determine the sample mass and placed in an aluminum DSC pan, and then the lid of the DSC pan is sealed using a crimping press. The DSC is configured to run from -100°C to 225°C with a heating rate of 20°C/minute, hold at 225°C for 2 minutes and then cool to room temperature (e.g. 25°C) with a scan rate of -10 °C/minute. The enthalpy of fusion is calculated by integrating the area of the peak melting endotherm and normalizing by the sample mass.

Water Uptake Test Protocol

This test measures the water absorbency of the sheet material after a predetermined soaking time for a sample (e.g., taken using the footwear sampling method discussed above). The sample is initially dried at 60°C until there is no weight change for consecutive measurement intervals at least 30 minutes apart (e.g. a drying period of 24 hours at 60°C is typically a suitable duration). The total weight of the dried sample (Wt, _{Sample Dry} ) is then measured in grams. The dried sample is allowed to cool to 25°C and is fully immersed in a deionized water bath maintained at 25°C. After a given soaking time, the sample is removed from the deionized water bath, blotted with a cloth to remove surface water, and the total weight of the soaked sample (Wt, _{sample wet} ) is measured in grams.

Any suitable soak time may be used, with a 24 hour soak time being assumed to simulate saturation conditions for the layered material of the present disclosure (i.e. the hydrophilic resin will be in its saturated state). Accordingly, as used herein, the term "having a water absorbency at 5 minutes" refers to a soaking time of 5 minutes, the term "having a water absorbing capacity at 1 hour" refers to a soaking time of 1 hour, the term "having a water absorbing capacity at Having 24 hours” refers to a soaking time of 24 hours and the like. Where no time period is specified following a water absorption capacity value, the soak period corresponds to a 24 hour period.

It is understood that the total weight of a sample taken in accordance with the footwear sampling procedure must include the weight of the dried or soaked material (Wt, _{sample dry} or Wt, _{sample wet} ) and the weight of the substrate (Wt, _substrate ). be subtracted from the sample measurements.

The weight of the substrate (Wt, _substrate ) is calculated using the sample surface area (eg, 4.0 cm ² ), an average measured thickness of the sheet material, and the average density of the sheet material. Alternatively, if the density of the material for the substrate is not known or available, the weight of the substrate (Wt, _substrate ) is determined by taking a second sample using the same sampling method as used for the primary sample and with the same dimensions (surface area and film/substrate thicknesses) as determined for the primary sample. The second sample material is then cut away from the second sample substrate with a blade to provide an insulated substrate. The isolated substrate is then dried at 60°C for 24 hours, which can be done simultaneously with the drying of the primary sample. The weight of the insulated substrate (Wt, _substrate ) is then measured in grams.

$${\text{Wt }}_{\text{Komponente nass}}=\text{Wt}{\mathrm{,,}}_{\text{Probe nass}}-\text{Wt}{\text{,}}_{\text{Substrat}}$$

The resulting substrate weight (Wt, _substrate ) is then subtracted from the dried and soaked primary sample weights (Wt,, _{sample dry} or Wt, _{sample wet} ) to give the dried and soaked material weights (Wt, , _{component dry} or Wt , _{component wet} ) as represented by Equations 1 and 2. $$\text{Wt}{\text{.}}_{\text{component dry}}=\text{Wt}{\mathrm{,,}}_{\text{sample dry}}-\text{Wt}{\text{,}}_{\text{substrate}}$$

$${\text{Wt}}_{\text{component wet}}=\text{Wt}{\mathrm{,,}}_{\text{sample wet}}-\text{Wt}{\text{,}}_{\text{substrate}}$$

The weight of the dried component (Wt. _{component dry} ) is then subtracted from the weight of the saturated component (Wt _{component wet} ) to provide the weight of water picked up by the component, which is then divided by the weight of the dried component (Wt _{component dry} ) is divided to provide the water uptake capacity for the given soak time as a percentage, as represented by Equation 3 below. $$\text{water absorption capacity}\ddot{\text{O}}\text{gene}=\frac{{\text{Wt}}_{\text{component wet}}-\text{Wt}{\text{.}}_{\text{component dry}}}{\text{Wt}{\text{.}}_{\text{component dry}}}\left(100\%\right)$$

For example, a water absorbency of 50% at 1 hour means that the impregnated component weighed 1.5 times its dry weight after soaking for 1 hour. Similarly, a water absorbency of 500% at 24 hours means that the impregnated component weighed 5 times its dry weight after soaking for 24 hours.

Water Uptake Rate Test Protocol

This test measures the water uptake rate of the sheet material by modeling weight gain versus soak time for a sample with a one-dimensional diffusion model. The sample may be taken using any of the sampling methods discussed above, including the footwear sampling method. The sample is dried at 60°C until there is no change in weight for consecutive measurement intervals at least 30 minutes apart (a drying period of 24 hours at 60°C is usually a suitable duration). The total weight of the dried sample (Wt i , _{sample dry} ) is then measured in grams. In addition, the average component thickness for the dried sample is measured for use in calculating the water uptake rate, as discussed below.

The dried sample is allowed to cool to 25°C and is fully immersed in a deionized water bath maintained at 25°C. Between soak periods of 1, 2, 4, 9, 16, and 25 minutes, the sample is removed from the deionized water bath, blotted with a tissue to remove surface water, and the total weight of the soaked sample (Wt,, _{sample wet} ) is measured, where "t" refers to the specified soak duration data point (e.g., 1, 2, 4, 9, 16, or 25 minutes).

The exposed surface area of the soaked sample is also measured with calipers to determine specific gravity gain, as discussed below. Exposed surface area refers to the surface area in contact with the deionized water when fully immersed in the bath. For samples obtained using the footwear sampling method, the samples have only one major surface exposed. For the sake of simplicity, the surface areas of the peripheral edges of the sample are ignored due to their relatively small dimensions.

The measured sample is completely re-immersed in the deionized water bath between measurements. The durations of 1, 2, 4, 9, 16, and 25 minutes refer to increasing soak times while the sample is fully immersed in the deionized water bath (i.e., after the first minute of soaking and the first measurement, the sample is returned to the bath for an additional minute of soaking before measuring at the 2 minute benchmark).

As discussed above in the Water Uptake Test, the total weight of a sample taken in accordance with the Footwear Sampling Procedure includes the weight of the dried or soaked material (Wt _{component wet} or Wt _{component dry} ) and the weight of the article or backing substrate (Wt, _substrate ). To determine a weight change in the material due to water uptake, the weight of the substrate (Wt, _substrate ) must be subtracted from the sample weight measurements. This can be accomplished using the same steps discussed in the Water Uptake Test above to calculate the resulting material weights Wt, _{Component Wet} , and Wt. Provide _{component dry} for each soaking duration measurement.

wobei t sich auf den bestimmten Tränkungsdauerdatenpunkt (z. B. 1, 2, 4, 9, 16 oder 25 Minuten) bezieht, wie oben erwähnt.The specific gravity gain (Ws _t ) of water uptake for each soaked sample is then calculated as the difference between the weight of the soaked sample (Wt _{component wet} ) and the weight of the initial dried sample (Wt _{component dry} ), the resulting difference then being given by is divided by the exposed surface area of the soaked sample (At) as shown in Equation 4. $$\left({\text{Ws}}_{\text{t}}\right)=\frac{\left({\text{Wt}}_{\text{component wet}}-\text{Wt}{\text{.}}_{\text{component dry}}\right)}{\left({\text{A}}_{\text{t}}\right)}$$

where t refers to the particular soak duration data point (e.g., 1, 2, 4, 9, 16, or 25 minutes) as noted above.

The water uptake rate for the elastomeric material is then determined as the slope of the specific gravity increases (Ws _t ) compared to the square root of time (in minutes) as determined by a least squares linear regression of the data points. For the elastomeric material of the present disclosure, the plot of specific gravity increases (Ws _t ) compared to the square root of time (in minutes) provides an initial slope that is essentially linear (to provide the water uptake rate by linear regression analysis). However, after a period of time that depends on the thickness of the component, the specific gravity increases slow down, indicating a reduction in the water uptake rate, until the saturated state is reached. This is believed to be due to the water being sufficiently diffused throughout the elastomeric material as water uptake approaches saturation, and will vary with component thickness.

Therefore, for the component with an average thickness (as measured above) less than 0.3 millimeters, only the specific weight gain data points at 1, 2, 4 and 9 minutes are used in the linear regression analysis. In these cases, the data points at 16 and 25 minutes may begin to deviate significantly from the linear slope - due to the water intake approaching saturation - and are omitted from the linear regression analysis. In comparison, for the component with an average dried thickness (as measured above) of 0.3 millimeters or more, the specific gravity increase data points at 1, 2, 4, 9, 16, and 25 minutes are used in the linear regression analysis. The resulting slope, which defines the water uptake rate for the sample, has units of weight/(surface area-square root of time), such as grams/(meter ² -minutes ^1/2 ) or g/m ² /√min.

Furthermore, some component surfaces can create surface phenomena that rapidly attract and retain water molecules (e.g., via surface hydrogen bonding or capillary action) without actually drawing the water molecules into the film or substrate. Thus, samples of these films or substrates can show rapid specific gravity increases for the 1-minute sample and possibly for the 2-minute sample. After that, however, further weight gain is negligible. Therefore, linear regression analysis is only applied if the specific gravity gain at 1, 2, and 4 minute data points continues to show an increase in water uptake. If this is not the case, the water uptake rate is considered to be approximately zero g/m ² /√min under this test methodology.

Source Asset Test Protocol

This test measures the component's ability to swell in terms of increases in thickness and volume after a given soaking time for a sample (e.g., taken with the footwear sampling method discussed above). The sample is initially dried at 6°C until there is no weight change for consecutive measurement intervals at least 30 minutes apart (a drying period of 24 hours is usually a suitable duration). The dimensions of the dried sample are then measured (eg, thickness, length, and width for a rectangular sample; thickness and diameter for a circular sample, etc.). The dried sample is then fully immersed in a deionized water bath maintained at 25°C. After a given soaking time, the sample is removed from the deionized water bath, blotted with a cloth to remove surface water, and the same dimensions for the soaked sample are again measured.

Any suitable soaking time can be used. Accordingly, as used herein, the term "having an increase in swelling thickness (or volume) at 5 minutes from" refers to a soaking time of 5 minutes, the term "having an increase in swelling thickness (or volume) at 1 hour from." ' refers to a test duration of 1 hour, the phrase "exhibiting an increase in swelling thickness (or volume) at 24 hours of" refers to a test duration of 24 hours, and the like.

Component swelling is determined by (1) an increase in thickness between the dried and impregnated components, (2) an increase in volume between the dried and impregnated components, or (3) both. The increase in caliper between the dried and impregnated components is determined by subtracting the measured caliper from the initial dried Component calculated from the measured thickness of the impregnated component. Similarly, the increase in volume between the dried and impregnated components is calculated by subtracting the measured volume of the initial dried component from the measured volume of the impregnated component. The increases in caliper and volume can also be presented as percentage increases relative to dry caliper and dry volume, respectively.

contact angle test

This test measures the contact angle of the sheet material based on a static sessile drop contact angle measurement for a sample (e.g., taken with the footwear sampling method or coextruded film sampling method discussed above). Contact angle refers to the angle at which a liquid interface meets a solid surface and indicates how hydrophilic the surface is.

For a dry test (i.e. to determine a contact angle when dry), the sample is initially equilibrated at 25°C and 20% humidity for 24 hours. For a wet test (i.e., to determine a contact angle when wet), the sample is completely immersed in a bath of deionized water maintained at 25°C for 24 hours. Thereafter, the sample is removed from the bath and blotted with a tissue to remove surface water and, if necessary, clamped onto a glass slide to prevent curling.

The dry or wet sample is then placed on a moving stage of a contact angle goniometer commercially available under the tradename "RAME-HART F290" from Rame-Hart Instrument Col, Sussasunna, N.J. A 10 microliter drop of deionized water is then placed onto the sample using a syringe and automatic pump. An image of the drop is then immediately captured (before the film can capture the drop) and the contact angle of both edges of the water drop is measured from the image. The reduction in contact angle between the dried and wet samples is calculated by subtracting the measured contact angle of the wet sheet material from the measured contact angle of the dry sheet material.

Coefficient of Friction Test

This test measures the coefficient of friction of the Coefficient of Friction test for a sample (e.g., taken with the footwear sampling method, coextruded film sampling method, or bare film sampling method discussed above). For a dry test (i.e., to determine a coefficient of friction when dry), the sample is initially equilibrated at 25°C and 20% humidity for 24 hours. For a wet test (i.e., to determine a coefficient of friction when wet), the sample is completely immersed in a bath of deionized water maintained at 25°C for 24 hours. Thereafter, the sample is removed from the bath and blotted with a cloth to remove surface water.

The measurement is performed with an aluminum sled mounted on an aluminum test rail and used to perform a sliding friction test for a test sample on an aluminum surface of the test rail. The test rail measured 127 millimeters wide by 610 millimeters long. The aluminum slide measured 76.2 millimeters by 76.2 millimeters with a 9.5 millimeter radius cut into the leading edge. The contact area of the aluminum sled with the rail was 76.2 millimeters x 66.6 millimeters or 5100 square millimeters.

The dry or wet sample is attached to the bottom of the sled using a two part thermosetting epoxy adhesive commercially available under the trade name "LOCTITE 608" from Henkel, Dusseldorf, Germany. The adhesive is used to maintain the flatness of the wet sample, which may curl when saturated. A polystyrene foam about 25.4 millimeters thick is attached to the top surface of the sled (opposite the test sample) for structural support.

The sliding friction test is performed using a screw driven load frame. A pull rope is attached to the sled, supporting a bracket in the structural polystyrene foam support, and wrapped around a pulley to pull the sled over the aluminum test rail. The sliding or frictional force is measured using a force transducer with a capacitance ity of 2000 Newtons. Normal force is controlled by placing weights on the aluminum sled supported by the structural polystyrene foam support for a total sled weight of 20.9 kilograms (205 Newtons). The traverse of the test frame is increased at a rate of 5 mm/second and the total test displacement is 250 mm. The coefficient of friction is calculated based on the equilibrium force parallel to the direction of motion required to pull the carriage at a constant speed. The coefficient of friction itself is found by dividing the equilibrium traction force by the applied normal force. Any transient value related to the static coefficient of friction at the start of the test is ignored.

memory module test

This test measures the sheet material's resistance to deformation (ratio of stress to strain) when a vibrational or oscillating force is applied to it and is a good indicator of film compliance in both dry and wet conditions. For this test, a sample is provided in bare form using the bare film sampling method modified such that the surface area of the test sample is rectangular with dimensions 5.35 millimeters wide and 10 millimeters long. The sheet material thickness can range from 0.1 millimeters to 2 millimeters and the specific range is not particularly limited since the final modulus result is normalized according to the sheet material thickness.

The storage modulus (E'), in units of megapascals (MPa), of the sample is determined by dynamic mechanical analysis (DMA) using a DMA analyzer commercially available under the tradename "Q800 DMA ANALYZER" from TA Instruments, New Castle, Del ., which is equipped with a relative humidity accessory to keep the sample at a constant temperature and relative humidity during analysis.

Initially, the thickness of the test sample is measured using vernier calipers (for use in modulus calculations). The test sample is then clamped into the DMA analyzer, which is operated with the following stress/strain conditions during analysis: isothermal temperature of 25°C, frequency of 1 Hertz, strain amplitude of 10 microns, preload of 1 Newton, and force trace of 125 %. The DMA analysis is performed at a constant temperature of 25°C according to the following time/relative humidity (RH) profile: (i) 0% RH for 300 minutes (representing the dry condition for storage modulus determination), (ii) 50% RH for 600 minutes, (iii) 90% RH for 600 minutes (representing the wet condition for storage modulus determination) and (iv) 0% RH for 600 minutes.

The E' value (in MPa) is determined from the DMA curve according to standard DMA techniques at the end of each time segment with a constant RH value. The E' value at 0% RH (i.e. the dry storage modulus) is the value at the end of step (i), the E' value at 50% RH is the value at the end of step (ii) and the E ' value at 90% RH (i.e. the wet storage modulus) is the value at the end of step (iii) in the specified time/relative humidity profile.

The sheet material may be characterized by its dry storage modulus, its wet storage modulus, or the reduction in storage modulus between the sheet material when dry and when wet, where the wet storage modulus is less than the dry storage modulus. This reduction in storage modulus can be reported as a difference between the dry storage modulus and the wet storage modulus, or as a percentage change relative to the dry storage modulus.

glass transition temperature test

This test measures the glass transition temperature (T _g ) of the outsole film for a sample where the outsole film is provided in bare form, such as with the bare film sampling method or the bare material sampling method, with a sample weight of 10 milligrams. The sample is measured in both a dry state and a wet state (ie, after exposure to a humid environment as described herein).

The glass transition temperature is determined by DMA using a DMA analyzer commercially available under the trade name "Q2000 DMA ANALYZER" from TA Instruments, New Castle, Del., equipped with airtight aluminum pans and the sample chamber is purged with 50 millimeters/minute of nitrogen gas during analysis. Samples in the dry state are prepared by holding at 0% RH to constant weight (less than 0.01% weight change over a 120 minute period). Wet samples are prepared by conditioning at a constant 25°C according to the following time/relative humidity (RH) profile: (i) 250 minutes at 0% RH, (ii) 250 minutes at 50% RH and (iii) 1440 minutes at 90% RH. Step (iii) of the conditioning program may be terminated early if the sample weight is measured during conditioning and it is found to be substantially constant within 0.05% over a 100 minute interval.

After the sample is prepared in either the dry or wet state, it is analyzed by DSC to provide a curve of heat flow versus temperature. The DSC analysis is performed with the following time/temperature profile: (i) equilibrate at -90°C for 2 minutes, (ii) ramp at +10°C/minute to 250°C, (iii) ramp at - 50°C/minute to -90°C and (iv) ramp at +10°C/minute to 250°C. The glass transition temperature value (in Celsius) is determined from the DSC curve according to standard DSC techniques.

sampling procedure

Various properties of the resin compositions and plaques and other articles molded therefrom can be characterized using samples prepared with the following sampling methods:

Material Sampling Procedure

A material sampling method can be used to obtain a clean sample of a resin composition or, in some cases, a sample of a material used to mold a resin composition. The material is provided in media form such as flakes, granules, powder, pellets and the like. If a source of the resin composition is not available in a pure form, the sample can be cut from a panel or other component containing the resin composition, thereby isolating a sample of the material.

Plaque Sampling Procedure

Polyolefin resin is combined with the effective amount of polymeric resin modifier along with any additional components to form the resin composition. A portion of the resin composition is then formed into a plaque by thermoforming the resin composition in a mold sized to fit the Ross Cold Bend Tester used, the plaque measuring approximately 15 centimeters (cm) by 2.5 centimeters ( cm) and a thickness of from about 1 millimeter (mm) to about 4 millimeters (mm). The sample is made by mixing the components of the resin composition, melting the components, pouring or injecting the melted composition into the mold cavity, cooling the mixed composition to solidify it in the mold cavity to form the plaque, and then taking out the solid plaque made from the mold cavity.

definitions

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains. It is further understood that terms, as used in commonly used dictionaries, are to be understood as having a meaning consistent with their meaning in the context of the specification and the relevant art, and not in an idealized or excessive manner should be construed in the formal sense unless expressly defined herein.

All publications, patents, and patent applications cited in this specification are cited to disclose and describe the methods and/or materials cited in connection with the publications. All such publications, patents and patent applications are incorporated herein by reference as if each individual publication or patent were specifically and individually indicated as being incorporated by reference. Such incorporation by reference is expressly limited to the methods and/or materials set forth in the publications, patents and patent applications cited, and does not extend to any lexicographical definitions contained in the publications, patents and patent applications cited. Any lexicographical definition in the cited publications, patents and patent applications that is not further expressly repeated in the present specification should not be treated as such and should not be construed to mean any term appearing in the accompanying claims, is defined.

While any methods and materials that are the same or equivalent to those described herein can be used in the practice or testing of the present disclosure, preferred methods and materials are now described. Functions or constructions well known in the art may not be described in detail for the sake of brevity and/or clarity. Aspects of the present disclosure employ techniques within the capabilities of the art in nanotechnology, organic chemistry, materials science, engineering, and the like unless otherwise noted. Such techniques are fully explained in the literature.

Note that ratios, concentrations, amounts, and other numeric data may be expressed herein in a range format. Where the stated range includes one or both limits, ranges excluding either or both of those included limits are also included in the disclosure, e.g. For example, the expression "x to y" includes the range from "x" to "y" and the range greater than "x" and less than "y". The range can also be expressed as an upper limit, e.g. B. "about x, y, z or less" and should be interpreted as including the specific ranges "about x", "about y" and "about z" as well as the ranges "less than x", "less than y ' and 'less than z'. Likewise, the phrase "about x, y, z or more" should be interpreted to include the specific ranges "about x", "about y" and "about z" as well as the ranges "more than x", "more than y ' and 'more than z'. Additionally, the phrase "about 'x' to 'y'" where 'x' and 'y' are numeric values includes "about 'x' to about 'y'". It should be understood that such a range format is used for the sake of convenience and brevity and should therefore be interpreted in a flexible manner to include not only the numeric values explicitly stated as the boundaries of the range, but also any individual numeric values or sub-ranges which are included in this range, as if each numerical value and subrange is explicitly named. To illustrate: A number range from "about 0.1% to about 5%" should be interpreted in such a way that it not only includes the explicitly mentioned values of about 0.1% to about 5%, but also individual values (e.g. 1%, 2%, 3% and 4%) and the sub-ranges (e.g. 0.5%, 1.1%, 2.4%, 3.2% and 4.4%) within the specified range .

The term "providing," as used herein and as referred to in the claims, is not intended to require any particular delivery or receipt of the provided item. Rather, the term “providing” is used merely to list matter referred to in later elements of the claim(s) for purposes of clarity and ease of reading. As used herein, the terms "Material Sampling Method", "Plate Sampling Method", "Ross Cold Bending Test", "ASTM D 5963-97a" and "Differential Scanning Calorimeter (DSC) Test" refer to the respective sampling methods and test methods used are described in the section "Property Analysis and Characterization Methods". These sampling procedures and test methods characterize the properties of said materials, films, articles and components and the like and need not be performed as active steps in the claims.

The term "about" as used herein may involve conventional rounding after significant digits of the numerical value. In some aspects, for example, the term is used herein to indicate a deviation of 10%, 5%, 2.5%, 1%, 0.5%, 0.1%, 0.01% or less from the specified value.

The articles "a", "an" and "an" as used herein mean one or more when applied to any feature in aspects of the present disclosure described in the specification and claims. The use of "a", "an" and "an" does not limit the meaning to a single feature, unless such limitation is expressly stated. The articles "der", "die" or "das" preceding singular or plural nouns or noun clauses denote a certain specified feature or features and may, depending on the context in which they are used, take a singular or plural form have plural meaning.

A propylene random copolymer containing about 2.2 weight percent (wt%) ethylene is commercially available under the tradename "PP9054" from ExxonMobil Chemical Company, Houston, TX. It has an MFR (ASTM-1238D, 2.16 kilograms, 230°C) of about 12 grams/10 minutes and a density of 0.90 grams/cubic centimeter (g/cm ³ ).

PP9074 is a propylene random copolymer containing about 2.8 weight percent (wt%) ethylene and is commercially available under the tradename "PP9074" from ExxonMobil Chemical Company, Houston, TX. It has an MFR (ASTM-1238D, 2.16 kilograms, 230°C) of about 24 grams/10 minutes and a density of 0.90 grams/cubic centimeter (g/cm ³ ).

PP1024E4 is a propylene homopolymer commercially available under the trade name "PP1024E4" from ExxonMobil Chemical Company, Houston, TX. It has an MFR (ASTM-1238D, 2.16 kilograms, 230°C) of about 13 grams/10 minutes and a density of 0.90 grams/cubic centimeter (g/cm ³ ).

Vistamaxx 6202 is a copolymer consisting primarily of isotactic propylene repeat units with about 15% by weight ethylene repeat units randomly distributed along the copolymer. It is a metallocene-catalyzed copolymer available under the tradename "VISTAMAXX 6202" from ExxonMobil Chemical Company, Houston, TX and has an MFR (ASTM-1238D, 2.16 kilograms, 230°C) of about 20 grams/10 minutes and a density of 0.862 grams/cubic centimeter (g/cm ³ ) and a durometer of about 64 (Shore A).

Vistamaxx™ 3000 is a copolymer composed primarily of isotactic propylene repeat units with approximately 11% by weight ethylene repeat units randomly distributed along the copolymer. It is a metallocene-catalyzed copolymer available from ExxonMobil Chemical Company and has an MFR (ASTM-1238D, 2.16 kilograms, 230°C) of about 8 grams/10 minutes and a density of 0.873 grams/cubic centimeter (g/cm ³ ) and has a durometer of about 27 (Shore D).

Vistamaxx™ 6502 is a copolymer consisting primarily of isotactic propylene repeat units with approximately 13% by weight ethylene repeat units randomly distributed along the copolymer. It is a metallocene-catalyzed copolymer available from ExxonMobil Chemical Company and has an MFR (ASTM-1238D, 2.16 kilograms, 230°C) of about 45 grams/10 minutes and a density of 0.865 grams/cubic centimeter (g/cm ³ ) and has a durometer of about 71 (Shore A).

EXAMPLES

Having generally described aspects of the present disclosure, the following examples describe some additional aspects of the present disclosure. While aspects of the present disclosure are described in connection with the following examples and the corresponding text and figures, there is no intention to limit aspects of the present disclosure to this description. On the contrary, the intention is to cover all alternatives, modifications, and equivalents as may be included within the spirit and scope of the present disclosure.

materials

The following base resins were used for the examples described below. Table 1: Base resins Description of the base resin Polyolefin base resin supplier MFI Description PP9054 ExxonMobil 12 Propylene random copolymer PP9074Med ExxonMobil 24 Propylene random copolymer/high clarity PP1024E4 ExxonMobil 13 propylene homopolymer

The following polymeric resin modifiers were used in the examples. Table 2: Polymeric resin modifiers Description of the modifier(s)/mixture Polymeric resin modifier supplier MFI loading % ethylene percent Vistamaxx 6202 ExxonMobil 21 30 15 Vistamaxx 3000 ExxonMobil 9.1 50 11 Vistamaxx 6502 ExxonMobil 43 40 13

The resin compositions, including the base resins and varying amounts of polymeric resin modifiers, were prepared and tested to determine abrasion loss according to ASTM D 5963-97a using the material sampling method and by a flex test according to the Ross cold flex test using the plate sampling method. The results are shown in Table 3. Percent (%) crystallization was measured for samples of the resin compositions using a DSC test using the material sampling method. The results are shown in Table 4. Table 3: Density, DIN Abrasion Loss and Ross Cold Bend Test Summary of Resin Compositions with Different Levels of Polymeric Resin Modifiers Polyolefin base resin base resin wt% Polymeric resin modifier tel Resin modifier wt% Ross cold bend test summary 9 density DIN abrasion loss (cm3) PP9054 100 no 0 failed 0.896 0.089 PP9054 85 6202 15 stocks 0.891 0.085 PP9054 70 6202 30 * 0.891 0.095 PP9054 50 6202 50 * 0.883 0.158 PP9054 85 6502 15 * 0.896 0.084 PP9054 80 6502 20 stocks * * PP9054 60 6502 40 * * * PP9054 85 3000 15 * 0.897 0.078 PP9054 75 3000 25 stocks * * PP9054 50 3000 50 * * * PP9074Med 100 no 0 failed 0.902 0.089 PP9074Med 85 6202 15 * 0.894 0.101 PP9074Med 70 6202 30 stocks * * PP1024E4 100 no 0 stocks 0.903 0.083 PP1024E4 85 6202 15 * 0.899 0.162 PP1024E4 50 3000 50 stocks * *
* not determined Table 4. Percent crystallization of representative resin compositions base resin base resin wt% blend resin Blend resin wt% % Crystallization PP9054 100 no 0 38% PP9054 85 6202 15 34% PP9054 70 6202 30 30% PP9054 80 6502 20 24% PP9054 60 6502 40 24% PP9054 75 3000 25 29% PP9054 50 3000 50 23% PP9074Med 100 no 0 45% PP9074Med 70 6202 30 30% PP1024E4 100 no 0 54% PP1024E4 50 3000 50 30%

It should be emphasized that the aspects of the present disclosure described above are only possible examples of implementation and are presented only for a clear understanding of the principles of the disclosure. Many variations and modifications can be made to the aspects of the disclosure described above without materially departing from the spirit and principles of the disclosure. All such modifications and variations are intended to be included within the scope of this disclosure.

The present disclosure will be better understood upon review of the following features, which should not be confused with the claims.

Feature 1. A sole structure for an article of footwear, the sole structure comprising: a plate comprising a polyolefin resin, the plate having a first side and a second side, the first side being configured to face the ground when the plate is a component an article of footwear; and a textile provided on one or both of the first and second sides.

Feature 2. The sole structure of any one of Features 1-105, wherein the textile is on the second side.

Feature 3. The sole structure of any one of features 1-105, further comprising a lower chassis, the lower chassis being configured to be on the first side of the plate.

Feature 4. The sole structure of any one of features 1-105, wherein the lower chassis is configured to wrap around the plate and engage or attach to an upper when the sole structure is a component of an article of footwear.

Feature 5. The sole structure of any one of Features 1-105, wherein the lower chassis is configured to be attached to the upper at the line of engagement when the sole structure is a component of an article of footwear.

Feature 6. The sole structure of any one of Features 1-105, wherein the lower chassis comprises a polymer selected from the group consisting of polypropylene, polypropylene/polyethylene copolymers, copolymers of ethylene and higher olefins such as polyethylene/polyoctene copolymers , copolymers thereof including one or more additional polymers, as well as mixtures thereof.

Feature 7. The sole structure of any one of features 1-105, wherein the chassis comprises a polyolefin.

Feature 8. The sole structure of any of Features 1-105, wherein the chassis comprises a resin composition of any of Features 130-194.

Feature 9. The sole structure of any one of features 1-105, wherein the textile is on the first side of the panel and wherein the textile comprises a patterned or decorative textile.

Feature 10. The sole structure of any of Features 1-105, wherein the textile is on the first side of the panel and wherein an adhesion strength of the first side to the chassis is greater than an adhesion strength of the otherwise same plate to the otherwise same chassis except without the textile, using the otherwise same gluing process.

Feature 11. The sole structure of any one of features 1-105, wherein the fabric comprises a first fabric on the first side of the panel and a second fabric on the second side of the panel.

Feature 12. The sole structure of any one of features 1-105, wherein the first textile and the second textile are different.

Feature 13. The sole structure of any one of features 1-105, wherein the first fabric and the second fabric are identical.

Feature 14. The sole structure of any one of features 1-105, wherein the sole structure is configured to extend from a medial side to a lateral side of the article of footwear when the sole structure is a component of an article of footwear.

Feature 15. The sole structure of any one of features 1-105, wherein a length of the plate is configured to extend through a metatarsal region to a midfoot region of the article of footwear when the sole structure is a component of an article of footwear.

Feature 16. The sole structure of any one of features 1-105, wherein a length of the plate is configured to extend through a midfoot region to a heel region of the article of footwear when the sole structure is a component of an article of footwear.

Feature 17. The sole structure of any one of features 1-105, wherein a length of the plate is configured to extend from a toe region to a heel region of the article of footwear when the sole structure is a component of an article of footwear.

Feature 18. The sole structure of any one of features 1-105, wherein the first side of the panel includes traction elements.

Feature 19. The sole structure of any one of features 1-105, wherein the traction elements are integrally formed in the plate.

Feature 20. The sole structure of any one of Features 1-105, wherein the traction elements include the injection molded resin composition.

Feature 21. The sole structure of any one of features 1-105, wherein the chassis includes traction elements on the side of the chassis configured to face the ground when the sole structure is a component of a footwear article.

Feature 22. The sole structure of any one of features 1-105, wherein the traction elements are integrally formed in the chassis.

Feature 23. The sole structure of any one of features 1-105, wherein the first side of the panel includes one or more apertures configured to receive a detachable traction element.

Feature 24. The sole structure of any one of features 1-105, wherein the chassis includes one or more openings configured to receive a removable traction element on a side of the chassis configured to face the ground when the sole structure is a component of an article of footwear.

Feature 25. The sole structure of any one of features 1-105, wherein the traction elements comprise a second resin different from the polyolefin resin.

Feature 26. The sole structure of any one of Features 1-105, wherein the second resin is a polystyrene, a polyethylene, an ethylene-α-olefin copolymer, an ethylene-propylene rubber (EPDM), a polybu ten, a polyisobutylene, a poly-4-methylpent-1-ene, a polyisoprene, a polybutadiene, an ethylene-methacrylic acid copolymer, an olefin elastomer, a copolymer thereof, or a blend or blend thereof.

Feature 27. The sole structure of any one of features 1-105, wherein the second resin comprises about 20%, about 10% or less of a polyolefin.

Feature 28. The sole structure of any one of features 1-105, wherein the second resin comprises about 20%, about 10% or less polypropylene.

Feature 29. The sole structure of any one of features 1-105, wherein the second resin comprises an ethylene propylene rubber (EPDM) dispersed in polypropylene.

Feature 30. The sole structure of any one of features 1-105, wherein the second resin comprises a block copolymer comprising a polystyrene block.

Feature 31. The sole structure of any one of features 1-105, wherein the block copolymer comprises a copolymer of styrene and ethylene and/or butylene.

Feature 32. Sole structure according to any one of features 1-105, wherein the textile is formed by injection molding the sheet on the textile, by laminating the textile to the sheet, by welding the textile to the sheet and/or by gluing to the sheet using an adhesive applied to the plate.

Feature 33. The sole structure of any of Features 1-105, wherein the fabric is selected from the group consisting of a woven fabric, a nonwoven fabric, a knitted fabric, a braided fabric, and a combination thereof.

Feature 34. The sole structure of any one of features 1-105, wherein the textile comprises one or more fibers comprising a polymer selected from the group consisting of a polyester, a polyamide, a polyolefin, a mixture thereof, and a combination thereof.

Feature 35. The sole structure of any one of features 1-105, wherein the textile comprises a yarn comprising the fibers.

Feature 36. The sole structure of any one of features 1-105, wherein a surface roughness of the surface comprising the textile is greater than a surface roughness of the otherwise same surface except without the textile.

Feature 37. The sole structure of any of Features 1-105, wherein the sheet comprises a resin composition of any of Features 130-194.

Feature 38. The sole structure of any one of features 1-105, wherein the sheet further comprises a clearing agent.

Feature 39. The sole structure of any one of features 1-105, wherein the clarifier is present in an amount of from about 0.5% to about 5%, or from about 1.5% by weight, based on a total weight of the polyolefin resin. -% to about 2.5% by weight is present.

Feature 40. The sole structure of any one of Features 1-105, wherein the clarifier is selected from the group consisting of substituted or unsubstituted dibenzylidene sorbitol, 1,3-O-2,4-bis(3,4-dimethylbenzylidene) sorbitol, 1 ,2,3-Trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene] and a derivative thereof.

Feature 41. The sole structure of any one of Features 1-105, wherein the clarification agent comprises an acetal compound that is the condensation product of a polyhydric alcohol and an aromatic aldehyde.

Feature 42. The sole structure of any one of features 1-105, wherein the polyhydric alcohol is selected from the group consisting of acyclic polyols such as xylitol and sorbitol and acyclic deoxypolyols such as 1,2,3-trideoxynonitol or 1,2,3-trideoxynone -1-enit exists.

Feature 43. The sole structure of any one of features 1-105, wherein the aromatic aldehyde is selected from the group consisting of benzaldehyde and substituted benzaldehydes.

Feature 44. A sole structure for an article of footwear, the sole structure comprising: a plate comprising a polyolefin resin, the plate having a first side and a second side, the first side being configured to face the ground when the plate has a is a component of an article of footwear; and a chassis, the chassis configured to be on the first side of the panel.

Feature 45. The sole structure of any one of features 1-105, wherein the chassis is configured to wrap around the plate and engage or attach to an upper when the sole structure is a component of an article of footwear.

Feature 46. The sole structure of any one of features 1-105, wherein the chassis is configured to be attached to the upper at the line of engagement when the sole structure is a component of an article of footwear.

Feature 47. The sole structure of any one of features 1-105, wherein the chassis comprises a polymer selected from the group consisting of polypropylene, polypropylene/polyethylene copolymers, copolymers of ethylene and higher olefins such as polyethylene/polyoctene copolymers, copolymers thereof include one or more additional polymers, as well as mixtures thereof.

Feature 48. The sole structure of any one of features 1-105, wherein the chassis comprises a polyolefin.

Feature 49. The sole structure of any of Features 1-105, wherein the chassis comprises a resin composition of any of Features 130-194.

Feature 50. The sole structure of any one of features 1-105, wherein the chassis comprises a second resin different from the polyolefin resin.

Feature 51. The sole structure of any one of Features 1-105, wherein the second resin is a polystyrene, a polyethylene, an ethylene-α-olefin copolymer, an ethylene-propylene rubber (EPDM), a polybutene, a polyisobutylene, a poly -4-methylpent-1-ene, a polyisoprene, a polybutadiene, an ethylene-methacrylic acid copolymer, an olefin elastomer, a copolymer thereof, or a blend or blend thereof.

Feature 52. The sole structure of any one of features 1-105, wherein the second resin comprises about 20%, about 10% or less of a polyolefin.

Feature 53. The sole structure of any one of features 1-105, wherein the second resin comprises about 20%, about 10% or less polypropylene.

Feature 54. The sole structure of any one of features 1-105, wherein the second resin comprises an ethylene propylene rubber (EPDM) dispersed in polypropylene.

Feature 55. The sole structure of any one of features 1-105, wherein the second resin comprises a block copolymer comprising a polystyrene block.

Feature 56. The sole structure of any one of features 1-105, wherein the block copolymer comprises a copolymer of styrene and ethylene and/or butylene.

Feature 57. The sole structure of any one of features 1-105, wherein the sole structure is configured to extend from a medial side to a lateral side of the article of footwear when the sole structure is a component of an article of footwear.

Feature 58. The sole structure of any one of features 1-105, wherein a length of the plate is configured to extend through a metatarsal region to a midfoot region of the article of footwear when the sole structure is a component of an article of footwear.

Feature 59. The sole structure of any one of features 1-105, wherein a length of the plate is configured to extend through a midfoot region to a heel region of the article of footwear when the sole structure is a component of an article of footwear.

Feature 60. The sole structure of any one of features 1-105, wherein a length of the plate is configured to extend from a toe region to a heel region of the article of footwear when the sole structure is a component of an article of footwear.

Feature 61. The sole structure of any one of features 1-105, wherein the first side of the panel includes traction elements.

Feature 62. The sole structure of any one of features 1-105, wherein the traction elements are integrally formed in the plate.

Feature 63. The sole structure of any one of features 1-105, wherein the traction elements include the injection molded resin composition.

Feature 64. The sole structure of any one of features 1-105, wherein the chassis includes traction elements on the side of the chassis configured to face the ground when the sole structure is a component of a footwear article.

Feature 65. The sole structure of any one of features 1-105, wherein the traction elements are integrally formed in the chassis.

Feature 66. The sole structure of any one of features 1-105, wherein the chassis includes one or more openings configured to receive a detachable traction element on a side of the chassis configured to face the ground when the sole structure is a component of an article of footwear.

Feature 67. The sole structure of any of Features 1-105, wherein the sheet comprises a resin composition of any of Features 130-194.

Feature 68. The sole structure of any one of features 1-105, wherein the sheet further comprises a clearing agent.

Feature 69. The sole structure of any one of features 1-105, wherein the clarifying agent is present in an amount of from about 0.5% to about 5%, or from about 1.5% by weight, based on a total weight of the polyolefin resin % to about 2.5% by weight.

Feature 70. The sole structure of any one of Features 1-105, wherein the clarifier is selected from the group consisting of a substituted or unsubstituted dibenzylidene sorbitol, 1,3-O-2,4-bis(3,4-dimethylbenzylidene) sorbitol, 1,2,3-Trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene] and a derivative thereof.

Feature 71. The sole structure of any one of Features 1-105, wherein the clarification agent comprises an acetal compound that is the condensation product of a polyhydric alcohol and an aromatic aldehyde.

Feature 72. The sole structure of any one of features 1-105, wherein the polyhydric alcohol is selected from the group consisting of acyclic polyols such as xylitol and sorbitol and acyclic polyols such as 1,2,3-trideoxynonitol or 1,2,3-trideoxy -1-enitol.

Feature 73. The sole structure of any one of features 1-105, wherein the aromatic aldehyde is selected from the group consisting of benzaldehyde and substituted benzaldehydes.

Feature 74. The sole structure of any one of features 1-105, wherein the first side of the panel comprises a hydrogel material.

Feature 75. The sole structure of any one of features 1-105, wherein the hydrogel material comprises a polyurethane hydrogel.

Feature 76. The sole structure of any one of features 1-105, wherein the polyurethane hydrogel is a reaction polymer of a diisocyanate with a polyol.

Feature 77. The sole structure of any one of features 1-105, wherein the hydrogel material comprises a polyamide hydrogel.

Feature 78. The sole structure of any one of Features 1-105, wherein the polyamide hydrogel is a reaction polymer of a condensation of diamino compounds with dicarboxylic acids.

Feature 79. The sole structure of any one of features 1-105, wherein the hydrogel material comprises a polyurea hydrogel.

Feature 80. The sole structure of any one of features 1-105, wherein the polyurea hydrogel is a reaction polymer of a diisocyanate with a diamine.

Feature 81. The sole structure of any one of features 1-105, wherein the hydrogel material comprises a polyester hydrogel.

Feature 82. The sole structure of any one of Features 1-105, wherein the polyester hydrogel is a reaction polymer of a dicarboxylic acid with a diol.

Feature 83. The sole structure of any one of features 1-105, wherein the hydrogel material comprises a polycarbonate hydrogel.

Feature 84. The sole structure of any one of features 1-105, wherein the polycarbonate hydrogel is a reaction polymer of a diol with a carbonate diester.

Feature 85. The sole structure of any one of Features 1-105, wherein the hydrogel material comprises a polyetheramide hydrogel.

Feature 86. The sole structure of any one of features 1-105, wherein the polyetheramide hydrogel is a reaction polymer of dicarboxylic acid and polyetherdiamine.

Feature 87. The sole structure of any one of features 1-105, wherein the hydrogel material comprises a hydrogel composed of addition polymers of ethylenically unsaturated monomers.

Feature 88. The sole structure of any one of features 1-105, wherein the hydrogel material comprises a hydrogel formed from a copolymer, the copolymer being a combination of two or more types of polymers within each polymer chain.

Feature 89. The sole structure of any one of features 1-105, wherein the copolymer is selected from the group consisting of: a polyurethane/polyurea copolymer, a polyurethane/polyester copolymer, and a polyester/polycarbonate copolymer.

Feature 90. The sole structure of any one of features 1-105, wherein the sole structure comprises the chassis and wherein the chassis or a side of the chassis configured to face the ground when the sole structure is a component of an article of footwear, comprising the hydrogel material.

Feature 91. The sole structure of any one of features 1-105, wherein the hydrogel material exhibits a water circulation weight loss of from about 0% to about 15% by weight as measured by the water circulation test using the component sampling method.

Feature 92. The sole structure of any one of features 1-105, wherein the hydrogel material exhibits a water recirculation weight loss of less than about 15% by weight as measured by the water recirculation test using the component sampling method.

Feature 93. The sole structure of any one of features 1-105, wherein the hydrogel material has a circulating water weight loss of less than 10% by weight.

Feature 94. The sole structure of any one of features 1-105, wherein the hydrogel material has a dry thickness in the range of about 0.2 mm to about 2.0 mm.

Feature 95. The sole structure of any one of features 1-105, wherein the hydrogel material has a saturated thickness that is at least 100% greater than the dry thickness of the hydrogel material.

Feature 96. The sole structure of any one of features 1-105, wherein the thickness of the hydrogel material in the saturated state is at least 200% greater than the thickness of the hydrogel material in the dry state.

Feature 97. The sole structure of any one of features 1-105, wherein the sole structure has a ground-facing side and the hydrogel material is affixed to the ground-facing side of the sole structure.

Feature 98. The sole structure of any one of features 1-105, wherein the textile is on the ground-facing side of the sole structure, and wherein the textile is a knitted textile, a woven textile, a fiber composite textile, a braided textile, or a combination thereof.

Feature 99. The sole structure of any one of features 1-105, wherein the sole structure further comprises an adhesive, primer, or tie layer interposed between the ground-facing side and the hydrogel material or the elastomeric material.

Feature 100. The sole structure of any one of features 1-105, wherein the adhesive, the primer, and/or the bonding layer comprises/comprise a polymer having epoxy segments, urethane segments, acrylic segments, cyanoacrylate segments, silicone segments, or any combination thereof.

Feature 101. The sole structure of any one of Features 1-105, wherein the polyolefin resin of the sheet, the adhesive, the primer and/or the tie layer comprises/comprise a polymer having maleic anhydride functional groups.

Feature 102. The sole structure of any one of features 1-105, wherein the sheet, adhesive, primer and/or tie layer comprises maleic anhydride.

Feature 103. The sole structure of any one of Features 1-105, wherein the adhesive, primer, or tie layer comprises a thermoplastic polyurethane.

Feature 104. The sole structure of any one of features 1-105, wherein the ground-facing side of the sole structure has a texture.

Feature 105. The sole structure of any one of features 1-105, wherein the ground-facing side of the sole structure formed from the hydrogel material has a mud-shedding force that is less than about 12 Newtons as determined by the mud-shedding test using the component sampling method.

Feature 106. An article of footwear comprising an upper and sole structure according to any one of Features 1-105.

Feature 107. The article of footwear of any of features 106-110, wherein the article has a mechanical bond between the plate and the upper.

Feature 108. The article of footwear of any of features 106-110, wherein the article has an adhesive bond between the surface comprising the textile and the upper.

Feature 109. The article of footwear of any of features 106-110, wherein the article has a mechanical bond between the chassis and the upper.

Feature 110. The article of footwear of any of features 106-110, wherein one or more of the resin composition of the plate, the resin composition of the chassis, and a polymeric material of the upper are fused together.

Feature III. A method of making a component for an article of footwear or athletic equipment, the method comprising disposing a textile on a surface of a polyolefin resin composition.

Feature 112. The method of any one of Features 111-118, comprising injection molding the resin composition onto the textile.

Feature 113. The method of any one of Features 111-118, comprising laminating the textile to a surface of the resin composition, welding the textile to a surface of the resin composition, and/or bonding to a surface of the resin composition using an adhesive.

Feature 114. The method of any one of Features 111-118, wherein the fabric is selected from the group consisting of a woven fabric, a fiber composite fabric, a knitted fabric, a braided fabric, and a combination thereof.

Feature 115. The method of any one of features 111-118, wherein the textile comprises one or more fibers comprising a polymer selected from the group consisting of a polyester, a polyamide, a polyolefin, a mixture thereof, and a combination of these.

Feature 116. The method of any one of features 111-118, wherein the textile comprises a yarn comprising the fibers.

Feature 117. The method of any one of features 111-118, wherein a surface roughness of the surface comprising the textile is greater than a surface roughness of the otherwise same surface except without the textile.

Feature 118. The method of any of Features 111-118, wherein the resin composition comprises a resin composition of any of Features 130-194.

Feature 119. A method of making a sole structure, the method comprising placing a textile on a surface of a panel, the panel comprising a polyolefin resin composition.

Feature 120. The method of any one of features 119-129, comprising injection molding the sheet onto the textile.

Feature 121. The method of any one of features 119-129, comprising laminating the textile to a surface of the panel, welding the textile to a surface of the panel, and/or bonding to a surface of the panel using an adhesive.

Feature 122. The method of any of Features 119-129, wherein the fabric is selected from the group consisting of a woven fabric, a fiber composite fabric, a knitted fabric, a braided fabric, and a combination thereof.

Feature 123. The method of any one of features 119-129, wherein the textile comprises one or more fibers comprising a polymer selected from the group consisting of a polyester, a polyamide, a polyolefin, a mixture thereof, and a combination of these.

Feature 124. The method of any one of features 119-129, wherein the textile comprises a yarn comprising the fibers.

Feature 125. The method of any one of features 119-129, wherein a surface roughness of the surface comprising the textile is greater than a surface roughness of the otherwise same surface except without the textile.

Feature 126. The method of any of Features 119-129, wherein the resin composition comprises a resin composition of any of Features 130-194.

Feature 127. The method of any one of features 119-129, further comprising placing the plate in a chassis configured to be on the ground-facing side of the chassis when the sole structure is a component of an article of footwear.

Feature 128. The method of any one of features 119-129, further comprising injection molding the plate into a chassis configured to be on the ground-facing side of the chassis when the sole structure is a component of an article of footwear.

Feature 129. The method of any of features 119-129, wherein the chassis is injection molded prior to injection molding of the panel.

Feature 130. A resin composition comprising: a polyolefin copolymer and an effective amount of a polymer resin modifier.

Feature 131. The resin composition of any of Features 130-194, wherein the resin composition has an abrasion loss of from about 0.05 cubic centimeters to about 0.1 cubic centimeters or from about 0.08 cubic centimeters to about 0.1 cubic centimeters according to ASTM D 5963-97a using of the material sampling procedure.

Feature 132. The resin composition of any one of Features 130-194, wherein the effective amount of the polymeric resin modifier is an amount effective to allow the resin composition to pass a flexure test according to the Ross Cold Bend Test using the plaque sampling method.

Feature 133. The resin composition of any one of Features 130-194, wherein the effective amount of the polymeric resin modifier is an amount effective to make the resin composition without an appreciable change in attrition loss compared to attrition loss of a second resin composition comprising the resin composition apart therefrom equal to having no polymer resin modifier, when measured according to ASTM D 5963-97a using the material sampling method, can pass a flexure test according to the Ross Cold Bend Test using the plaque sampling method.

Feature 134. The resin composition of any one of Features 130-194, wherein the abrasion loss of the resin composition is from about 0.08 cubic centimeters to about 0.1 cubic centimeters.

Feature 135. The resin composition of any one of Features 130-194, wherein the polyolefin copolymer is a random copolymer.

Feature 136. The resin composition of any of Features 130-194, wherein the polyolefin copolymer comprises a plurality of repeating units, each of the plurality of repeating units being individually derived from an alkene monomer having from about 1 to about 6 carbon atoms.

Feature 137. The resin composition of any of Features 130-194, wherein the polyolefin copolymer comprises a plurality of repeating units, each of the plurality of repeating units being individually derived from a monomer selected from the group consisting of ethylene, propylene , 4-methyl-1-pentene, 1-butene and a combination thereof.

Feature 138. The resin composition of any one of Features 130-194, wherein the polyolefin copolymer comprises a plurality of repeating units each individually selected from Formulas 1A-1D.

worin R¹ ein Wasserstoff oder ein substituiertes oder unsubstituiertes, lineares oder verzweigtes C₁-C₁₂-Alkyl oder -Heteroalkyl ist.Feature 139. The resin composition according to any one of Features 130-194, wherein the polyolefin copolymer comprises a plurality of repeating units each individually having a structure according to formula 2,

wherein R ¹ is a hydrogen or a substituted or unsubstituted, linear or branched C ₁ -C ₁₂ alkyl or heteroalkyl.

Feature 140. The resin composition of any one of Features 130-194, wherein polymers in the resin composition essentially comprise polyolefin copolymers.

Feature 141. The resin composition of any of Features 130-194, wherein the polyolefin copolymer is a random copolymer of a first plurality of repeating units and a second plurality of repeating units and wherein each repeating unit in the first plurality of repeating units is derived from ethylene and each repeat unit in the second plurality of repeat units is derived from a second olefin.

Feature 142. The resin composition of any of Features 130-194, wherein the second olefin is selected from the group consisting of propylene, 4-methyl-1-pentene, 1-butene, and other linear or branched terminal alkenes having from about 3 to about 12 carbon atoms.

Feature 143. The resin composition of any one of Features 130-194, wherein each of the repeating units in the first plurality of repeating units has a structure according to Formula 1A and wherein each of the repeating units in the second plurality of repeating units has a structure selected from the formulas 1B-1D.

worin R¹ ein Wasserstoff oder ein substituiertes oder unsubstituiertes, lineares oder verzweigtes C₂-C₁₂-Alkyl oder -Heteroalkyl ist.Feature 144. The resin composition of any one of Features 130-194, wherein each of the repeating units in the first plurality of repeating units has a structure according to Formula 1A and wherein each of the repeating units in the second plurality of repeating units has a structure according to Formula 2,

wherein R ¹ is a hydrogen or a substituted or unsubstituted, linear or branched C ₂ -C ₁₂ alkyl or heteroalkyl.

Feature 145. The resin composition of any one of Features 130-194, wherein, based on a total weight of the polyolefin copolymer, the polyolefin copolymer is about 80% to about 99%, about 85% to about 99%, about 90% to about 99% % or about 95% to about 99% polyolefin repeat units.

Feature 146. The resin composition of any one of Features 130-194, wherein, based on a total weight of the polyolefin copolymer, the polyolefin copolymer is from about 1% to about 5%, from about 1% to about 3%, from about 2% to about 3% % or about 2% to about 5% ethylene.

Feature 147. The resin composition of any one of Features 130-194, wherein the polyolefin copolymer is substantially free of polyurethanes.

Feature 148. The resin composition of any of Features 130-194, wherein polymer chains of the polyolefin copolymer are substantially free of urethane repeat units.

Feature 149. The resin composition of any one of features 130-194, wherein the resin composition is substantially free of polymer chains comprising urethane repeat units.

Feature 150. The resin composition of any one of Features 130-194, wherein the polyolefin copolymer is substantially free of polyamide.

Feature 151. The resin composition of any of Features 130-194, wherein polymer chains of the polyolefin copolymer are substantially free of amide repeat units.

Feature 152. The resin composition of any one of Features 130-194, wherein the resin composition is substantially free of polymer chains comprising amide repeat units.

Feature 153. A resin composition comprising: a polypropylene copolymer and an effective amount of a polymer resin modifier.

Feature 154. The resin composition of any of Features 130-194, wherein the resin composition has an abrasion loss of from about 0.05 cubic centimeters (cm ³ ) to about 0.1 cubic centimeters (cm ³ ), about 0.07 cubic centimeters (cm ³ ) to about 0.1 cubic centimeters (cm ³ ), about 0.08 cubic centimeters (cm ³ ) to about 0.1 cubic centimeters (cm ³ ), or about 0.08 cubic centimeters (cm ³ ) to about 0.11 cubic centimeters (cm ³ ) according to ASTM D 5963-97a using the material sampling method.

Feature 155. The resin composition of any of Features 130-194, wherein the effective amount of the polymeric resin modifier is an amount effective to allow the resin composition to pass a flexure test according to the Ross Cold Bend Test using the plaque sampling method.

Feature 156. A resin composition comprising: a polypropylene copolymer and an effective amount of a polymer resin modifier.

Feature 157. The resin composition of any one of Features 130-194, wherein the effective amount of the polymeric resin modifier is an amount effective to make the resin composition without an appreciable change in attrition loss compared to attrition loss of a second resin composition comprising the resin composition apart therefrom equal to having no polymer resin modifier, measured according to ASTM D 5963-97a using the material sampling method, can pass a flexure test according to the Ross Cold Bend Test using the plaque sampling method.

Feature 158. The resin composition of any one of Features 130-194, wherein the abrasion loss of the resin composition is from about 0.05 cubic centimeters (cm ³ ) to about 0.1 cubic centimeters (cm ³ ), about 0.07 cubic centimeters (cm ³ ) to about 0 .1 cubic centimeters (cm ³ ), about 0.08 cubic centimeters (cm ³ ) to about 0.1 cubic centimeters (cm ³ ), or about 0.08 cubic centimeters (cm ³ ) to about 0.11 cubic centimeters (cm ³ ).

Feature 159. The resin composition of any one of Features 130-194, wherein the polypropylene copolymer is a random copolymer.

Feature 160. The resin composition of any one of Features 130-194, wherein, based on a total weight of the polypropylene copolymer, the polypropylene copolymer is about 80% to about 99%, about 85% to about 99%, about 90% to about 99% % or about 95% to about 99% polypropylene repeat units.

Feature 161. The resin composition of any one of Features 130-194, wherein, based on a total weight of the polypropylene copolymer, the polypropylene copolymer comprises from about 1% to about 5%, from about 1% to about 3%, from about 2% to about 3% % or about 2% to about 5% ethylene.

Feature 162. The resin composition of any of Features 130-194, wherein the polypropylene copolymer is a random copolymer comprising from about 2% to about 3% by weight, based on a total weight of the polypropylene copolymer, of a first plurality of repeat units and from about 80% to about 99% by weight of a second plurality of repeat units, each of the repeat units in the first plurality of repeat units having a structure according to Formula 1A and each of the repeat units in the second Variety of repeating units has a structure according to formula 1B.

Feature 163. The resin composition of any one of Features 130-194, wherein the polypropylene copolymer is substantially free of polyurethane.

Feature 164. The resin composition of any of Features 130-194, wherein polymer chains of the polypropylene copolymer are substantially free of urethane repeat units.

Feature 165. The resin composition of any of features 130-194, wherein the resin composition is substantially free of polymer chains comprising urethane repeat units.

Feature 166. The resin composition of any one of Features 130-194, wherein the polypropylene copolymer is substantially free of polyamide.

Feature 167. The resin composition of any of Features 130-194, wherein polymer chains of the polypropylene copolymer are substantially free of amide repeat units.

Feature 168. The resin composition of any one of features 130-194, wherein the resin composition is substantially free of polymer chains comprising amide repeat units.

Feature 169. The resin composition of any one of Features 130-194, wherein polymers in the resin composition essentially comprise propylene repeat units.

Feature 170. The resin composition of any one of Features 130-194, wherein polymers in the resin composition essentially comprise polypropylene copolymers.

Feature 171. The resin composition of any one of Features 130-194, wherein the polypropylene copolymer is a random copolymer of ethylene and propylene.

Feature 172. The resin composition of any one of Features 130-194, wherein the attrition loss of the resin composition, measured according to ASTM D 5963-97a using the material sampling method, is within about 20% of an attrition loss of the same resin composition (other than not having a resin modifier ) lies.

Feature 173. The resin composition of any of Features 130-194, wherein the resin composition, as measured according to the Differential Scanning Calorimeter (DSC) test using the Material Sampling Method, has a % crystallization of about 35%, about 30%, about 25% or less.

Feature 174. The resin composition of any of Features 130-194, wherein the resin composition exhibits a % crystallization that is at least 4 percentage points less than a % crystallization of the resin composition, as measured according to the DSC test using the Material Sampling Method is the same except that it has no polymer resin modifier.

Feature 175. The resin composition of any of Features 130-194, wherein the effective amount of the polymeric resin modifier, based on a total weight of the resin composition, is about 5% to about 30%, about 5% to about 25%, about 5% to about 20% , about 5% to about 15%, about 5% to about 10%, about 10% to about 15%, about 10% to about 20%, about 10% to about 25%, or about 10% to about 30%.

Feature 176. The resin composition of any of Features 130-194, wherein the effective amount of the polymeric resin modifier is about 20%, about 15%, about 10%, about 5%, based on a total weight of the resin composition.

Feature 177. The resin composition of any of Features 130-194, wherein the polymeric resin modifier comprises from about 10% to about 15% ethylene repeat units, based on the total weight of the polymeric resin modifier.

Feature 178. The resin composition of any one of Features 130-194, wherein the polymeric resin modifier comprises from about 10% to about 15%, based on a total weight of the polymeric resin modifier, of repeat units according to Formula 1A.

Feature 179. The resin composition of any one of Features 130-194, wherein the resin composition has a total ethylene repeat unit content of from about 3% to about 7%, based on a total weight of the resin composition.

Feature 180. The resin composition of any one of Features 130-194, wherein the polymeric resin modifier comprises from about 10% to about 15% ethylene repeat unit content, based on the total weight of the polymeric resin modifier.

Feature 181. The resin composition of any one of Features 130-194, wherein the polymeric resin modifier is a copolymer comprising isotactic repeating units derived from an olefin.

Feature 182. The resin composition of any one of Features 130-194, wherein the polymeric resin modifier is a copolymer comprising repeating units of Formula 1B and wherein the repeating units of Formula 1B are arranged in an isotactic, stereochemical configuration.

Feature 183. The resin composition of any one of Features 130-194, wherein a like resin composition (except for not having a polymer resin modifier) fails the Ross cold flex test using the material sampling method.

Feature 184. The resin composition of any one of Features 130-194, wherein the polymeric resin modifier is a copolymer comprising isotactic propylene repeating units and ethylene repeating units.

Feature 185. The resin composition of any one of Features 130-194, wherein the polymeric resin modifier is a copolymer comprising a first plurality of repeating units and a second plurality of repeating units, wherein each of the repeating units in the first plurality of repeating units has a structure according to Formula 1A and each of the repeating units in the second plurality of repeating units has a structure according to Formula 1B and wherein the repeating units are arranged in an isotactic, stereochemical configuration.

Feature 186. The resin composition of any one of Features 130-194, wherein the polymeric resin modifier is a catalyzed metallocene polymer.

Feature 187. The resin composition of any of Features 130-194, wherein the polymeric resin modifier is a catalyzed metallocene copolymer.

Feature 188. The resin composition of any of Features 130-194, wherein the polymeric resin modifier is a catalyzed metallocene propylene copolymer.

Feature 189. The resin composition of any one of Features 130-194, wherein the sheet further comprises a clarifying agent.

Feature 190. The resin composition of any one of features 130-194, wherein the clarifying agent is present in an amount of from about 0.5% to about 5%, or from about 1.5% by weight, based on a total weight of the polyolefin resin % to about 2.5% by weight.

Feature 191. The resin composition of any of Features 130-194, wherein the clarifier is selected from the group consisting of a substituted or unsubstituted dibenzylidene sorbitol, 1,3-O-2,4-bis(3,4-dimethylbenzylidene) sorbitol, 1,2,3-Trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene] and a derivative thereof.

Feature 192. The resin composition of any one of Features 130-194, wherein the clarifying agent comprises an acetal compound which is the condensation product of a polyhydric alcohol and an aromatic aldehyde.

Feature 193. The resin composition of any of Features 130-194, wherein the polyhydric alcohol is selected from the group consisting of acyclic polyols such as xylitol and sorbitol and acyclic polyols such as 1,2,3-trideoxynonitol or 1,2,3-trideoxy -1-enitol.

Feature 194. The resin composition of any of Features 130-194, wherein the aromatic aldehyde is selected from the group consisting of benzaldehyde and substituted benzaldehydes.

Claims (13)

Sole structure with a sheet containing a polyolefin resin, in which the polyolefin resin composition comprises a polyolefin copolymer and an effective amount of a polymer resin modifier, in which the effective amount of the polymer resin modifier, based on a total weight of the resin composition, is about 5% to about 30%, in which the polymer resin modifier is a copolymer comprising isotactic propylene repeat units and ethylene repeat units, and wherein the polymer resin modifier comprises from about 10% to about 15% ethylene repeat units based on the total weight of the polymer resin modifier. sole structure claim 1 , in which the polypropylene copolymer is a random copolymer. sole structure claim 1 or 2 wherein the polypropylene copolymer comprises from about 80% to about 99% polypropylene repeat units based on a total weight of the polypropylene copolymer. Sole structure according to one of Claims 1 until 3 wherein the polypropylene copolymer comprises from about 1% to about 5% ethylene based on a total weight of the polypropylene copolymer. Sole structure according to one of Claims 1 until 4 wherein the polymeric resin composition further comprises a clarifying agent. sole structure claim 5 wherein the clarifying agent is present in an amount of from about 0.5% to about 5% by weight, based on a total weight of the polyolefin resin. sole structure claim 5 or 6 wherein the clarifying agent is selected from the group consisting of a substituted or unsubstituted dibenzylidene sorbitol, 1,3-O-2,4-bis(3,4-dimethylbenzylidene) sorbitol, 1,2,3-trideoxy-4,6 :5,7-bis-O-[(4-propylphenyl)methylene] and a derivative thereof. sole structure claim 5 or 6 wherein the clarifying agent comprises an acetal compound which is the condensation product of a polyhydric alcohol and an aromatic aldehyde. A sole structure as claimed in any preceding claim, wherein the plate includes a first side and a second side, the first side being configured to face the ground when the plate is a component of an article of footwear. sole structure claim 9 further comprising a textile disposed on the first side and/or the second side. sole structure claim 9 or 10 , further comprising a chassis configured to be on the first side of the panel. sole structure claim 11 wherein the chassis is configured to wrap around the plate and engage or attach to an upper when the sole structure is a component of an article of footwear. Article of footwear comprising a sole structure according to any one of claims 9 until 12 and includes a shank.

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